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
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
  • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
• • 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
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene

Definitions

• the present invention relates to a novel priming system for the preparation of a living diene elastomer functionalized at the chain end by an amine group by anionic polymerization.
• the invention also relates to processes for the preparation of modified elastomers comprising at the end of the chain an amino group. These modified elastomers are particularly useful in reinforced tire rubber composition because they confer improved dynamic and mechanical properties in the vulcanized state.
• the reduction of the hysteresis of the mixtures is a permanent objective which must, however, be carried out while maintaining the ability to carry out the mixtures.
• many solutions have already been tested.
• the modified elastomers carrying an amine function at the end of the chain have the particularity of leading, thanks to the interaction of the amine function with the feedstock, to a reduction in the hysteresis of the mixture.
• This type of double functional elastomer initially requires the formation of a living polymer chain having an amino function at the chain end. This function is generally introduced by priming carried out using an amine functional species.
• NLi or N-Met with Met designating an alkali metal, not soubstituted in a hydrocarbon aliphatic solvent, is described in US 2,849,432, US 3,935,177, JP 59038209.
• the initiators described are of the type comprising a dialkylamine R 1 NR 2 N or a cycloalkylamine R 3 N (R 3 as well as R 1 R 2 alkylene group whose main chain contains a number of carbon atoms less than or equal to 6). They are known not to be soluble in hydrocarbon aliphatic solvents.
• the NLi species is formed initially by the reaction of an alkyl lithium on the secondary amine.
• Initiation using NLi species is carried out by dissolving NLi species in aliphatic solvents in EP 0 590 490, EP 0 593 049, EP 0 622 381, EP 0 626 278 and EP 0 718 321.
• Two routes have been developed to solubilize the NLi species, described "alone" insoluble in aliphatic solvent:
• N (monomer) x Li which can allow (co) polymerization of butadiene and styrene.
• RNLi R alkyl cyclic groups whose main chain contains more than 6 carbon atoms, soluble in aliphatic solvents is described in EPO 590 491, EP 0 600 208, EP 0 709 408 or EP 0 741 148 From a certain size (carbon number of the main chain greater than or equal to 7) the cyclic lithium amides are soluble in aliphatic solvents.
• the NLi species is formed by the reaction of an alkyl lithium on a secondary amine (RNH).
• the elastomer Being polymerization the elastomer is of the type (R 2 N -SRB-) 2 Sn- (R'-SBR) -Li. It contains both amine and tin functions. According to these authors, the addition of tin diamide on a living polymer chain does not lead to the deactivation.
• the initiators are soluble in aliphatic hydrocarbon solvents.
• the initiation by a species formed by the addition reaction of an alkyl lithium on the double bond of a compound having a tertiary amine function is described in EP 1 036 803, EP 1 334 985.
• This method requires the use of Diphenyl ethylene mono or di functional amine compounds.
• the reaction product of this species with an alkyllithium generates a tertiary alkyl mono or di functional amine which initiates the polymerization of styrene and butadiene.
• the object of the invention is to prepare living linear elastomers, modified at the end of the chain by an amine function, which are capable of being modified on the other end of the chain by a functionalising, coupling or starring agent .
• This goal is achieved in that the inventors have discovered a new priming system that allows both the synthesis of living elastomers functionalized with an amine group at the end of the chain and which has advantages in terms of industrial use because the initiators are soluble in the polymerization solvents.
• the inventors have demonstrated that when modifying the functionalized elastomer functionalized obtained with this new priming system, in particular by coupling with tin, it is possible to achieve reinforced rubber compositions with markedly reduced hysteresis. This improvement in hysteretic properties is particularly favorable for the use of such compositions for the manufacture of tires.
• a first object of the invention is a new priming system for the preparation of living diene elastomers functionalized with an amine group at the end of the chain, characterized in that it comprises an organolithium compound and a tetravalent tin amide.
• Another subject of the invention is a process for preparing a living diene elastomer functionalized with an amine group at the end of the chain, characterized in that it comprises a step of polymerizing at least one conjugated diene monomer by reaction with a priming system comprising an organolithium compound and a tin amide.
• the invention also relates to a method for preparing a modified diene elastomer comprising at the end (s) of chain (s) an amine function, said process comprising a first step of polymerization of at least one conjugated diene monomer by reaction with a priming system comprising an organolithium compound and a tin amide, followed by a step of modifying the living elastomer obtained in the preceding step by means of a modifying agent.
• any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range from a to b (i.e., including the strict limits a and b).
• the subject of the invention is therefore a new priming system for the preparation of living diene elastomers functionalized with an amine group at the end of the chain, characterized in that it comprises an organolithium compound and a tetravalent tin amide which does not has no tin-lithium bond, denoted Sn-Li.
• organolithium compound is meant according to the invention a hydrocarbon compound having a carbon-lithium bond represented by the formula RLi, wherein R represents an alkyl, aryl or cycloalkyl radical containing from 1 to 20 carbon atoms.
• R represents an alkyl, aryl or cycloalkyl radical containing from 1 to 20 carbon atoms.
• Preferred compounds are aliphatic organoliths. Among these representative compounds are ethyllithium, n-butyllithium (n-BuLi), isobutyl lithium.
• the tin amide is chosen from hexamethyleneimine tributyltin, pyrolidine tributyltin and 2-methylpyrolidine tributyltin.
• the initiator system according to the invention comprises the organolithium compound and tin amide in such proportions that the molar ratio of the organolithium compound to tin amide ranges from 1/1 to 8/1. It is preferable to introduce as many moles of organolithium compound as moles of amine groups present in tin amide, the molar ratio of the organolithium compound to the amine groups of the tin amide is preferably 1/1. These molar ratio values are given with an approximation due to the measurement uncertainty of about +/- 0.1.
• Another subject of the invention is a process for preparing a living diene elastomer functionalized with an amine group at the end of the chain, characterized in that it comprises a step of polymerizing at least one conjugated diene monomer by reaction with a priming system comprising an organolithium compound and a tin amide.
• diene elastomer is meant according to the invention any homopolymer obtained by polymerization of a conjugated diene monomer having 4 to 12 carbon atoms, or any copolymer obtained by copolymerization of one or more conjugated dienes with one another or with one or more compounds vinylaromatic compounds having 8 to 20 carbon atoms. In the case of copolymers, these contain from 20% to 99% by weight of diene units, and from 1 to 80% by weight of vinylaromatic units.
• 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di (C 1 to C 5) alkyl are particularly suitable.
• 3-butadiene 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, phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, etc.
• vinylaromatic compounds are especially suitable styrene, ortho-, meta, para-methylstyrene, the commercial mixture "vinyltoluene", para-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, etc.
• the diene elastomer is chosen from polybutadienes, butadiene-styrene copolymers, butadiene-styrene-isoprene copolymers and polyisoprene.
• the diene elastomer is a butadiene-styrene copolymer.
• polybutadienes and in particular those having a content (mol%) in units -1.2 of between 4% and 80% or those having a content (mol%) of cis-1,4 of greater than 80% are suitable, polyisoprenes, butadiene-styrene copolymers and in particular those having a Tg (glass transition temperature (Tg, measured according to ASTM D3418) between 0 ° C. and -80 ° C. and more particularly between -10 ° C. and -70 ° C.
• Tg glass transition temperature
• styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol%) in -1,2 bonds of the butadiene part of between 4% and 75%, a content (mol%) of trans-1,4 bonds of between 10% and 85%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg of -40 0 C to -80 0 C, isoprene-styrene copolymers and especially those having a styrene content of between 5% and 50% by weight and a Tg between 0 ° C.
• butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight, an isoprene content of between 15% and 60% by weight, and a butadiene content of between 5% and 50% by weight, and more generally any butadiene-styrene-isoprene copolymer having a Tg between - 20 0 C and - 70 0 C.
• the components of the initiation system are added to the polymerization medium, consisting of the monomer (s) and the solvent, separately, simultaneously or sequentially.
• the tin amide in the reaction medium before the introduction of the organolithium compound.
• the polymerization is carried out in the presence of an inert solvent, which may be an aliphatic or alicyclic hydrocarbon such as pentane, hexane, isooctane, cyclohexane, methylcyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene.
• an inert solvent which may be an aliphatic or alicyclic hydrocarbon such as pentane, hexane, isooctane, cyclohexane, methylcyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene.
• the mass ratio of the solvent to the monomer (s) before the polymerization reaction is preferably between 1 and 15, more preferably between 4 and 7.
• the polymerization process can be carried out continuously or discontinuously.
• the solution to be polymerized may also contain an ether-type polar agent, such as tetrahydrofuran, or an amine-type such as tetramethyl-ethylenediamine.
• ether-type polar agent such as tetrahydrofuran
• amine-type such as tetramethyl-ethylenediamine.
• polar agents can be used, among which non-chelating polar agents of THF type and chelating polar agents having on at least two atoms at least one non-binder doublet, for example of the tetrahydrofurfuryl ethyl ether or tetramethylethylenediamine type. Randomizing agents such as sodium alcoholates can also be added.
• the polymerization is generally carried out between 15 and 150 ° C., preferably between 30 and 100 ° C.
• a living diene elastomer functionalized with an amine group at the end of the chain is obtained.
• the polymerization can be stopped at the end of the reaction so as to obtain a diene elastomer functionalized with an amine group at the end of the chain.
• the stoppage is carried out in a manner known per se, for example by methanol or water.
• the polymerization can be stopped by a modifying agent, in a manner known per se, in order to obtain a modified diene elastomer comprising an amine group at the chain end.
• a modifying agent in a manner known per se, in order to obtain a modified diene elastomer comprising an amine group at the chain end.
• an object of the invention is constituted by a process for preparing a modified diene elastomer comprising at least one of its ends an amino function, said process comprising a first step of polymerization of at least one conjugated diene monomer by reaction with a priming system comprising an organolithium compound and tin amide, followed by a step of modifying the living elastomer obtained in the preceding step by means of a modifying agent.
• modified diene elastomer means an elastomer functionalized at the end of the chain, coupled or star-shaped by a group other than amine. This grouping comes from the modifying agent.
• an end-functionalized elastomer is a linear elastomer which comprises at one end of the chain an amine function and at the other end of the chain another function.
• a coupled elastomer is a linear elastomer composed of two elastomeric chains bonded together by a function other than amine, said elastomer comprises at each of its two ends an amine function.
• a star elastomer is composed of several (at least three) elastomeric branches bonded together by a function other than amine, said elastomer having at each of its branches an amine function. Modification agents for modifying the living elastomer obtained in the preceding polymerization step are known.
• coupling or starch functionalization agents of tin halide type of silicon.
• tin-based coupling agents type R 2 SnX 2 R an alkyl radical Ci-Ci 2 and X a halogen atom, preferably chlorine, for example Bu 2 SnCl 2 or a Bu 2 SnCl 2 mixture and SnCl 4 .
• the silicon-based coupling agents as described in the application in the name of the Applicants WO 08/141702 of the MeSiX 3 type (optionally in stoichiometry in order to carry out the synthesis of SBR having a silanol function in the middle of the chain), or as described in the applications on behalf of the Applicants FR 2 918 064 and FR 2 918 065 of the SiX 2 -polyether-SiX 2 type , X being a halogen atom, preferably chlorine .
• the functionalising, coupling or starring agents are capable of introducing a group comprising a polar function.
• This polar function can be chosen, for example, from silanol, alkoxysilane, alkoxysilane groups carrying an amino group, epoxide, ether, ester, hydroxyl or carboxylic acid.
• This function notably improves the interaction between the inorganic reinforcing filler of this type.
• a rubber composition and the elastomer Such modified elastomers are known per se and described in the prior art.
• the elastomers bearing a silanol function being located either at the end of the chain or in the middle of the chain.
• the silanol function can be carried by a polysiloxane block.
• Functionalized elastomers of this type are for example described in patent applications EP 0 778 311 A1, EP 0 786 493 A1, WO 08/141702, the disclosures of which are incorporated herein by reference.
• modified elastomers one or more carboxylic acid groups as described for example in the application WO 01/92402.
• Y represents the residues CH 2 - CH - R - or O CH
• R1 represents an alkyl, cycloalkyl or aryl radical having from 1 to 10 carbon atoms
• R2 represents an alkyl, aryl, cycloalkyl, alkaryl or aralkyl residue having from 1 to 12 carbon atoms
• - R3 represents an alkyl, aryl, alkaryl radical having from 1 to 12 carbon atoms
• - R4 represents a hydrocarbon residue having 1 to 6 carbon atoms and may comprise one or more oxygen atoms in the hydrocarbon chain
• n is an integer chosen from the values 0, 1,
• n is an integer chosen from the values 1 or 2
• p and q are integers chosen from the values 0, 1, 2, 3 or 4, provided that the sum p + q must represent an integer between 2 and 5 inclusively.
• end-functionalized elastomers coupled or stars resulting from the modification of the diene elastomers by an alkoxysilane-type agent carrying an amine group, cyclic or otherwise, tertiary, secondary or primary.
• Functionalized elastomers of this type are for example described in patent applications, US 2005/0203251, JP 2001158834, JP 2005232367, EP 1 457 501 A1, PCT / EP09 / 055061, the disclosures of which are incorporated herein by reference.
• the diene elastomer thus modified is coupled by an alkoxysilane group bonded to the diene elastomer by the silicon atom and carrying an amino grouperment.
• modified diene elastomer also means, according to the invention, a block elastomer comprising at least one polar block, the latter being more particularly a polyether block.
• block elastomers comprise at least said polar block at the end of the polymer chain or in the middle of the chain, or these block elastomers may be in star-shaped form with at least one central polar block to which several members are bonded, that is to say say more than two, polymeric chains.
• These block elastomers are generally obtained by reacting a living diene elastomer with a modifying agent having a functional polyether block.
• the amount of modifying agent is such that the molar ratio of modifying agent to the level of living polymer is between 0.25 and 1.0. We preferentially choose a ratio between 0.3 and 0.7.
• the modification reaction of the living diene elastomer may be carried out at a temperature of between -20 ° C. and 100 ° C., by adding the modifying agent to the living polymeric fasteners or vice versa. This reaction can of course be carried out with one or more modifying agents.
• the mixing of the living elastomer with the modifying agent may be carried out by any appropriate means, in particular with the aid of any mixer having static stirring and / or any perfectly agitated dynamic mixer known by the skilled in the art.
• the latter determines the reaction time between the living diene elastomer and the modifying agent. For example, this time can be between 10 seconds and 2 hours.
• one or more antioxidants can be added to the reaction mixture before recovery of the functionalized polymer.
• the modified polymer is separated from the reaction medium by conventional techniques, that is to say either by coagulation, or by steam distillation of the solvent, or by evaporation by any means such as for example evaporation under empty then dry if necessary.
• the process according to the invention makes it possible to obtain modified diene elastomers having a Mooney viscosity which can extend over a large scale of between 10 and 150 and preferably between 30 and 100.
• the modified diene elastomers obtained according to the process of the invention give the reinforced vulcanized rubber compositions containing them improved dynamic and mechanical properties. This makes these modified diene elastomers particularly suitable for producing a tire, more particularly a tire tread, particularly because of the low level of hysteresis achieved.
• the modified diene elastomers obtained according to the process of the invention also confer on the unvulcanized compositions containing the reinforcing filler satisfactory processing properties, in particular extrudability or drawability with the aid of a plodder compatible with the industrial tools.
• the reinforcing filler for forming these rubber compositions may be of any type suitable for pneumatic application, for example silica, carbon black or a black / silica blend.
• the coupled polymer obtained is subjected to an antioxidant treatment by adding 0.40 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.20 parts per hundred parts elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine. This polymer is recovered after stripping and drying on a cylinder tool.
• the inherent viscosity measured in toluene at 25 ° C. at a concentration of 0.1 g / dl of the obtained polymer is 1.85 dl / g.
• the ML viscosity of the polymer is 68.
• the mass ratio of 1,4-trans BR is 20.5%, that of 1,4-cis BR is 19,2% and that of BR 1,2 is 60,3%.
• the mass content of styrene is 25.4%.
• the molecular weight Mn of this polymer determined by the SEC technique, is 166,000 g / mol-1, PIP is 1.15.
• a sample is taken before the coupling reaction in a 250ml bottle containing an excess of methanol.
• the inherent viscosity of the sample which is measured at 25 ° C. in toluene at a concentration of 0.1 g / dl, is 1.18 dl / g.
• the molecular weight Mn determined by the SEC technique is 104,000 g / mol, the Ip is 1.15.
• the coupled polymer obtained is subjected to an antioxidant treatment by adding 0.80 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.20 parts per hundred parts elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine. This polymer is recovered after stripping and drying on a cylinder tool.
• the inherent viscosity measured in toluene at 25 ° C. at a concentration of 0.1 g / dl of the obtained polymer is 1.84 dl / g.
• the viscosity jump, ratio of the viscosity of the polymer coupled to the viscosity of the sample taken before coupling, is 1.56.
• the ML viscosity of the polymer is 68.
• the mass ratio of BR 1,4-trans is 20,3%, that of BR 1,4-cis is 19,0% and that of BR
• 1.2 is 60.7%.
• the mass content of styrene is 25.0%.
• the molecular weight Mn of this polymer determined by the SEC technique, is 174,000 g / mol, the Ip is 1.24.
• the level of tertiary amine groups bound to the polymer via a butadienyl 1,4 unit determined by 1 H NMR is 55%.
• a sample is taken before the coupling reaction in a 250ml bottle containing an excess of methanol.
• the inherent viscosity of the sample which is measured at 25 ° C. in toluene at a concentration of 0.1 g / dl, is 1.18 dl / g.
• the molecular weight Mn determined by the SEC technique is 101,000 g / mol, the Ip is 1.20.
• the coupled polymer obtained is subjected to an antioxidant treatment by adding 0.80 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.20 parts per hundred parts elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine. This polymer is recovered after stripping and drying on a cylinder tool.
• the inherent viscosity measured in toluene at 25 ° C. at a concentration of 0.1 g / dl of the obtained polymer is 1.77 dl / g.
• the viscosity jump, ratio of the viscosity of the polymer coupled to the viscosity of the sample taken before coupling, is 1.50.
• the ML viscosity of the polymer is 69.
• the mass ratio of 1,4-trans BR is 21.6%, that of 1,4-cis BR is 19.5% and that of BR 1,2 is 58.9%.
• the mass content of styrene is 24.8%.
• the molecular weight Mn of this polymer determined by the SEC technique, is 164,000 g / mol, the Ip is 1.25.
• a sample is taken before the coupling reaction in a 250ml bottle containing an excess of methanol.
• the inherent viscosity of the sample which is measured at 25 ° C in toluene at a concentration of 0.1 g / dl, is 1.12 dl / g.
• the molecular weight Mn determined by the SEC technique is 99,000 g / mol, the Ip is 1.10.
• the coupled polymer obtained is subjected to an antioxidant treatment by adding 0.80 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.20 parts per hundred parts elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine. This polymer is recovered after stripping and drying on a cylinder tool.
• the inherent viscosity measured in toluene at 25 ° C. at a concentration of 0.1 g / dl of the obtained polymer is 1.71 dl / g.
• the viscosity jump, ratio of the viscosity of the polymer coupled to the viscosity of the sample taken before coupling, is 1.53.
• the ML viscosity of the polymer is 70.
• the mass ratio of 1,4-trans BR is 20.5%, that of 1,4-cis BR is 19.5% and that of BR 1,2 is 60.0%.
• the mass content of styrene is 25.2%.
• the molecular weight Mn of this polymer determined by the SEC technique, is 164,000 g / mol, the Ip is 1.20.
• the four elastomers SBR A, SBR B, SBRC and SBR D were used for the preparation of rubber compositions A, B, C and D, each comprising carbon black and silica as a reinforcing filler. .
• compositions A, B, C and D has the following formulation (expressed in phr: parts per hundred parts of elastomer):
• compositions are carried out initially by thermomechanical work and then, in a second finishing time, by mechanical work.
• a laboratory internal mixer type "Banbury” the capacity of which is 400 cm3, which is filled to 75% and whose initial temperature is about 70 0 C, the elastomer, silica, oil, diphenylguanidine, X50S, antioxidant, stearic acid and wax then, about 40 seconds later, black, then, about three minutes later or at 150 0 C zinc monoxide.
• thermomechanical working stage is carried out for 5 to 6 minutes, until a maximum temperature of about 160 ° C. falls.
• the aforementioned first time of thermo-mechanical work is thus achieved, it being specified that the average speed of the pallets during this first time is 70 revolutions / min.
• compositions thus obtained are then calendered, either in the form of plates (with a thickness ranging from 2 to 3 mm) or thin rubber sheets, for the measurement of their physical or mechanical properties, or in the form of directly usable profiles, after cutting and / or assembly to the desired dimensions, for example as semi-finished products for tires, in particular for treads.
• the results are shown in the table below:
• compositions B, C and D according to the invention have a value of "Mooney mixture” equivalent to that of the composition A based on a non-functional elastomer.
• the elastomers B, C and D bearing an amine function and coupled tin according to the invention have an implementation equivalent to the non-crosslinked state to the non-functional elastomer.
• the MA300 / MA100 ratios of the compositions B, C and D according to the invention are greater than that of the composition A based on a non-functional elastomer.
• Elastomers B, C and D carrying an amino function and coupled tin according to the invention make it possible to improve the reinforcement with respect to the non-functional elastomer.
• the values of Delta G * and tan ⁇ max of the compositions B, C and D according to the invention are lower than those of the composition A based on a non-functional elastomer.
• the elastomers B, C and D carrying an amine function and coupled tin according to the invention allow to improve the hysteretic properties compared to the non-functional elastomer A.
• compositions B, C and D according to the invention based on elastomers bearing an amine function and coupled tin have rubber properties in the uncrosslinked state and in the crosslinked state which are improved by compared to those of the composition A based on a non-functional elastomer because of a significantly reduced hysteresis equivalent implementation.

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