Classifications

• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

• the present invention relates to reinforced rubber compositions based on natural rubber comprising at least one polyimine compound having improved hysteretic properties in the vulcanized state.
• These rubber compositions are intended for example for the manufacture of a semi-finished rubber product intended for tires of land and air vehicles. Since fuel savings and the need to protect the environment have become a priority, it has been necessary to produce tires with as low a rolling resistance as possible, without penalizing their wear resistance.
• patent application WO 96/37547 A1 describing a rubber composition using as reinforcing filler carbon black with silica fixed on its surface, based on a diene polymer functionalized or not and a silane coupling and coupling agent in a relatively large amount.
• the patent application JP2006063206A1 discloses the addition of polyimines, obtained by reaction of polyamines with a compound having a carbonyl function, to improve the abrasion resistance of compositions based on natural or synthetic rubbers containing an inorganic filler. as a single or predominant reinforcing filler or in cleavage with minor amount of carbon black and a silane coupling agent without significantly impairing the elongation and viscoelastic properties of the composition.
• compositions according to the invention based on natural rubber and a polyimine compound make them particularly suitable for the manufacture of semi-finished rubber products intended for tires, especially for land vehicles.
• motor-driven such as underlays, coating gums of metal or textile reinforcements, sidewall gums or treads.
• an object of the present invention is a reinforced rubber composition based at least on an elastomeric matrix comprising natural rubber, an organic or inorganic reinforcing filler or a blend of the two, a coupling agent when using an inorganic reinforcing filler and a polyimine compound of the following Formula 1 or 2:
• R 1 , R 2 which may be identical or different, are chosen from the group consisting of alkylidenes having from 1 to 20 carbon atoms, cycloalkylidenes having from 5 to 24 carbon atoms and arylidenes having from 6 to 18 carbon atoms, aralkylidenes having 7 to 25 carbon atoms and heterocycles, identical or different, having from 4 to 25 carbon atoms;
• R 4 , R 5, R 6 , R 7 which may be identical or different, are chosen from alkyl groups having from 1 to 20 carbon atoms, cycloalkyls having from 5 to 24 carbon atoms, aryls having from 6 to 18 carbon atoms or aralkyls having 7 to 25 carbon atoms;
• R3, Rs which may be identical or different, are chosen from the group consisting of alkylidenes having 1 to 20 carbon atoms, alkylidynes having 1 to 20 carbon atoms, alkylylidynes having 1 to 20 carbon atoms, cycloalkylidenes; having 5 to 24 carbon atoms, cycloalkylidyns having 5 to 24 carbon atoms, cycloalkylylidyns having 5 to 24 carbon atoms, arylidenes having 6 to 18 carbon atoms, arylidyns having 6 to 18 carbon atoms; carbon atoms, arylylidynes having 6 to 18 carbon atoms, aralkylidenes having 7 to 25 carbon atoms, aralkylidynes having 6 to 18 carbon atoms; carbon atoms, aralkylylidynes having from 6 to 18 carbon atoms, and heterocycles, identical or different, having from 4 to 25 carbon atoms;
• R3 optionally comprises one or more heteroatoms selected from O, N, S and Si.
• n 1 or 3
• n 1, 2 or 3
• Another object of the invention is a process for preparing such a reinforced rubber composition defined above.
• the invention also relates to a semi-finished tire rubber product consisting wholly or partly of the reinforced rubber composition defined above.
• Another object of the invention is a tire comprising at least one semi-finished rubber product consisting wholly or partly of the reinforced rubber composition as defined above.
• composition based on means a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with one another at least in part during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.
• 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).
• a first object of the invention is a reinforced rubber composition based at least on (a) an elastomeric matrix comprising at least predominantly natural rubber, (b) a reinforcing filler and (c) a polyimine compound having the following formula 1 or 2:
• R 1 , R 2 which may be identical or different, are chosen from the group consisting of alkylidenes having from 1 to 20 carbon atoms, cycloalkylidenes having from 5 to 24 carbon atoms and arylidenes having from 6 to 18 carbon atoms, aralkylidenes having 7 to 25 carbon atoms and heterocycles, identical or different, having from 4 to 25 carbon atoms;
• R 4 , R 5, R 6 , R 7 which may be identical or different, are chosen from alkyl groups having from 1 to 20 carbon atoms, cycloalkyls having from 5 to 24 carbon atoms, aryls having from 6 to 18 carbon atoms or aralkyls having 7 to 25 carbon atoms;
• R 3 , R 8 which may be identical or different, are chosen from the group consisting of alkylidenes having from 1 to 20 carbon atoms, alkylidynes having from 1 to 20 carbon atoms and alkylylidynes having from 1 to 20 carbon atoms; cycloalkylidenes having 5 to 24 carbon atoms, cycloalkylidines having at 24 carbon atoms, the cycloalkylylidynes having 5 to 24 carbon atoms, the arylidenes having 6 to 18 carbon atoms, the arylidynes having 6 to 18 carbon atoms, the arylylidynes having 6 to 18 carbon atoms, aralkylidenes having 7 to 25 carbon atoms, aralkylidyns having 6 to 18 carbon atoms, aralkylylidyns having 6 to 18 carbon atoms, and heterocycles, identical or different, having 4 to 25 carbon atoms;
• R3 optionally comprises one or more heteroatoms selected from O, N, S and Si.
• n 1 or 3
• n is equal to 1, 2 or 3
• polyimine compounds are preferably used compounds di-imines, triimines and tetraimines. These compounds and their method of preparation are described in the state of the art essentially to improve the abrasion resistance of rubber compositions intended for the manufacture of tires for vehicles, and patent application JP2006063206A1 may be cited in this respect. above, or for the preparation of resins according to the method described in US Patent 3,668,183.
• the polyimine compounds may for example be synthesized by condensing an amine on a ketone.
• This mode of preparing imines is described in "Advanced Organic Chemistry, Part B: Reactions and Synthesis” by FA Carey and RJ Sundberg, 4th Edition, pp 31-33, as well as in “Advanced Organic Chemistry, Reactions, Mechanisms, and Structure "by J. March, 5th Edition, pp 1185-1187 and in the references cited by these works.
• the amines used for the synthesis of the products corresponding to formula 1 can be for example:
• amines used for the synthesis of the products corresponding to formula 2 can be for example:
• melamine triethylenetetramine, tetraethylenepentamine, 2,2 ', 2 "-nitrilotriethylamine 3,6-dioxaoctane-1,8-diamine, N, N, N-tris (2-aminoethyl) amine, bis (3-aminopropyl) tetramethyldisiloxane, 2 - (2-aminoethoxy) ethanamine,
• ketones used for the synthesis of the products claimed in formulas 1 or 2 can be for example:
• Pentan-3-one 2,2,6,6-tetramethylcyclohexanone, 2,2,4,4-tetramethyl-3-pentanone, 4-methylpentan-2-one, 2,4-dimethylpentan-3-one, 2, 6-dimethylheptan-4-one, cyclohexanone, acetone, 2,6-dimethylcyclohexanone, 2,2,4,4-tetramethylpentan-3-one, (1 r, 3 ', 1 ") ter (cyclohexan) -2' -one, dicyclohexylmethanone, dicyclopentylmethanone, cyclopentanone, bicyclo [3.3.1] nonan-9-one, dicyclopropylmethanone, 2,6-di-tert-butyl-cyclohexanone, 2,6-dimethylcyclohexanone, 2,4-dimethyl-3-pentanone
• the polyimine compounds corresponding to formulas 1 or 2 are preferably chosen from those for which R 4 , R 5, R 0 and R 7 are each a hydrocarbon radical chosen from linear or branched, unsubstituted alkyl radicals.
• R 4 and R 1 are each a methyl radical
• R 5 and R 7 are each an isobutyl radical or the respective sets "R 4 , R 5" or “Re, R 7 " represent a cycloalkyl radical having 5 or 6 carbon atoms
• R 1 , R 2 and Rs are each a linear or branched, unsubstituted alkylidene radical having 2 to 8 carbon atoms or a cycloalkylidene radical having 6 carbon atoms
• R 3 is a unsubstituted alkylidene radical having 2 to 8 carbon atoms or an alkylidene radical having 2 to 6 carbon atoms having N as hetero atom.
• these polyimine compounds are chosen from N 5 N -Bis (4-methylpentan-2-ylidene) hexane-1,6-diamine, N, N'-bis (2,6-dimethylheptan-4-ylidene).
• the rubber composition of the tire component according to the invention comprises the polyimine compound in an amount of between 0 and 6 mmol per 100 g of elastomer, preferably ranging from 1 to 5 mmol per 100 g of elastomer, which is i.e. includes a low level of polyimine compound.
• the polyimine compound according to the invention is meant a compound or a mixture of several compounds corresponding to formulas 1 or 2.
• the elastomeric matrix of the composition is based on natural rubber. In some cases, the elastomeric matrix may advantageously consist entirely of natural rubber (100% of the elastomeric matrix is made of natural rubber).
• This variant is preferably implemented when it comes to using the rubber composition for manufacturing flanks, tire treads for commercial vehicles such as heavy goods vehicles or certain applications, such as ice or snow, of tourist vehicles, or to manufacture metal / rubber reinforcing composites, such as, for example, crown or carcass plies.
• the elastomeric matrix may also, in addition to the natural rubber, comprise at least one other diene elastomer. This or these other diene elastomers are then present in the matrix in proportions of between 0 and 50% by weight (the boundaries of this domain being excluded), preferably from 5% to 40%, even more preferably from 15% to 40% .
• the weight fraction of the natural rubber in the elastomeric matrix is the majority.
• the weight fraction is greater than or equal to 50% by weight of the total weight of the matrix, even more preferably 60% to 85% by weight of the total weight of the matrix.
• the majority weight fraction according to the invention is the highest weight fraction of the blend.
• the weight fractions in a ternary NR / elastomer A / elastomer B fraction, the weight fractions can be divided according to the proportions 45/30/25 or 40/40/20 or 40/30/30, the weight fractions being 45 or 40 respectively. and in a binary NR / elastomer cut, the weight fractions can be divided into 50/50 or 70/30 proportions, the majority weight fractions being 50 or 70.
• diene elastomer it is to be understood according to the invention any natural rubber, optionally functionalized, or any synthetic elastomer resulting at least in part from monomers dienes. More particularly, diene elastomer is 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 vinylaromatic compounds. having from 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.
• the optionally functionalized natural rubber is preferably an epoxidized rubber.
• the diene elastomer constituting a part of the elastomeric matrix according to the invention is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR), butadiene copolymers, polyisoprenes (PI) and isoprene copolymers. and mixtures of these elastomers.
• BR polybutadienes
• PI polyisoprenes
• isoprene copolymers and mixtures of these elastomers.
• Such copolymers are more preferably chosen from the group consisting of copolymers of butadiene and a vinylaromatic monomer, more particularly butadiene-styrene copolymer (SBR), isoprene-butadiene copolymers (BIR), copolymers of isoprene and a vinylaromatic monomer, more particularly the isoprene-styrene copolymer (SIR) and the isoprene-butadiene-styrene copolymers (SBIR).
• SBR butadiene-styrene copolymer
• BIR isoprene-butadiene copolymers
• SIR isoprene-butadiene copolymers
• SBIR isoprene-butadiene-styrene copolymers
• the diene elastomer constituting a part of the elastomeric matrix according to the invention may be star, coupled, functionalized or otherwise, in a manner known per se, by means of functionalising, coupling or staring agents known to man. art.
• the elastomers coupled according to the processes described in the claims on behalf of the Applicants WO 08/141702, FR 2 2910 64, FR 2 291 065 and FR 07/60442 may be mentioned.
• the rubber composition according to the invention comprises at least three compounds, including a reinforcing filler in proportions ranging from 35 to 200 phr.
• the total reinforcing filler content is between 40 and 140 phr, more preferably between 50 and 130 phr, the optimum being in a known manner different according to the particular applications of the tire concerned;
• the level of reinforcement expected on a bicycle tire is of course less than that required on a tire capable of running at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for a commercial vehicle such as than heavy weight.
• the reinforcing filler consists of a reinforcing organic filler such as carbon black or a reinforcing inorganic filler, such as reinforcing silica, in proportions ranging from 0 to 100% by weight of the total weight of the composition, or a blend organic filler / inorganic filler depending on the intended application.
• the proportion of organic or inorganic filler is respectively preferably greater than or equal to 50% by weight of the total weight of the composition, more particularly greater than 55% depending on the intended application.
• the second reinforcing filler contained in the blend (blend) of the majority reinforcing filler is then preferably present in a weight fraction of less than 50% relative to the total weight of the composition.
• -OH hydroxyl groups
• the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface area both less than 450 m 2 / g, even if the highly dispersible precipitated silicas are preferred.
• reinforcing inorganic filler mention may also be made of mineral fillers of the aluminous type, in particular alumina (Al2O3) or aluminum (oxide) hydroxides, or reinforcing titanium oxides.
• reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas as described above.
• reinforcing organic filler are suitable all carbon blacks, especially blacks of the type HAF, ISAF, SAF, FF, FEF, GPF and SRF conventionally used in tire rubber compositions (so-called pneumatic grade blacks).
• the reinforcing carbon blacks of the 100, 200 or 300 series for example the Nl 15, N134, N234, N326, N330, N339, N347 and N375 blacks, but also coarser blacks such as blacks N550 or N683. Carbon blacks could for example already be incorporated into natural rubber in the form of a masterbatch.
• Black / silica or partially or fully silica-coated blacks are suitable for the reinforcing filler.
• silica-modified carbon blacks such as, without limitation, the charges which are sold by CABOT under the name "CRX 2000", and which are described in the international patent document WO-A- 96/37547.
• reinforcing organic fillers other than carbon blacks
• the weight fraction of this carbon black in said reinforcing filler is more preferably less than or equal to 30% relative to the total weight of the reinforcing filler.
• the rubber composition according to the invention comprises at least four compounds, including a coupling agent for coupling the reinforcing inorganic filler to the natural rubber and to the possible diene elastomers that make up the matrix. elastomeric.
• coupling agent is more specifically meant an agent capable of establishing a sufficient chemical and / or physical bond between the charge in question and the elastomer, while facilitating the dispersion of this charge within the elastomeric matrix.
• a binding agent at least bifunctional, has for example as simplified general formula "Y-TX", in which: Y represents a functional group ("Y" function) which is capable of binding physically and / or chemically to the inorganic filler, such a bond can be established, for example, between a silicon atom of the coupling agent and the hydroxyl (-OH) surface groups of the inorganic filler (for example the surface silanols when this is silica);
• X ' represents a functional group ("X" "function) capable of bonding physically and / or chemically to the elastomer, for example via a sulfur atom; • T represents a divalent group making it possible to connect Y and X '.
• So-called inorganic filler particle coating agents may also be used. They are likely to further improve, by binding to the functional surface sites of the inorganic filler and thus covering it at least partially, the dispersion of the latter in the elastomeric matrix, thereby lowering its viscosity raw and improve overall its implementation implemented in the raw state.
• Such coating agents essentially belong to the family of polyols (for example diols, triols such as glycerol or its derivatives), polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanol-amines), hydroxylated or hydrolyzable polyorganosiloxanes, for example ⁇ , ⁇ -dihydroxy-polyorganosilanes (in particular ⁇ , ⁇ -dihydroxy-polydimethylsiloxanes), hydroxysilanes, alkylalkoxysilanes, in particular alkyltriethoxysilanes, for example 1-octyl -triethoxysilane marketed by Degussa-Evonik under the name "Dynasylan Octeo".
• polyols for example diols, triols such as glycerol or its derivatives
• polyethers for example polyethylene glycols
• coating agents are well known in pneumatic rubber compositions reinforced with an inorganic filler; they have been described, for example, in patent applications WO 00/05300, WO 01/55252, WO 01/96442, WO 02/031041, WO 02/053634, WO 02/083782, WO 03/002648, WO 03 / 002653, WO 03/016387, WO 2006/002993, WO 2006/125533, WO 2007/017060 and WO 2007/003408.
• the bonding agents should not be confused with simple charge-covering agents considered which, in a known manner, may have the active Y function with respect to the charge but lack the function X 'active vis-à-vis the charge.
• any binding agent known for, or capable of effectively ensuring, in the tire rubber compositions used for the manufacture of tires, the bonding (or coupling) between an inorganic reinforcing filler such as silica and a diene elastomer may be used.
• organosilanes in particular polysulfurized alkoxysilanes or mercaptosilanes, or else polyorganosiloxanes carrying the aforementioned X 'and Y functions.
• Silica / elastomer bonding agents in particular, have been described in a large number of documents, the best known of which are bifunctional alkoxysilanes such as polysulfurized alkoxysilanes.
• polysulfide silanes called “symmetrical” or “asymmetrical” silanes according to their particular structure, are used, as described for example in the applications WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650).
• polysulphide silanes mention may be made more particularly of polysulfides of bis (3-trimethoxysilylpropyl) or of bis (3-triethoxysilylpropyl).
• bis (3-triethoxysilylpropyl) tetrasulfide abbreviated as TESPT
• bis- (triethoxysilylpropyl) disulfide abbreviated as TESPD.
• polysulfides especially disulfides, trisulphides or tetrasulfides
• C1-C4 dialkyl
• silylpropyl more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide as described above. in the patent application WO 02/083782 (or US 2004/132880).
• coupling agent other than polysulfurized alkoxysilane there may be mentioned in particular bifunctional POSS (polyorganosiloxanes) or hydroxysilane polysulfides as described in patent applications WO 02/30939 (or US Pat. No. 6,774,255) and WO 02 / 31041 (or US 2004/051210), or silanes or POSS carrying azo-dicarbonyl functional groups, as described for example in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534.
• bifunctional POSS polyorganosiloxanes
• hydroxysilane polysulfides as described in patent applications WO 02/30939 (or US Pat. No. 6,774,255) and WO 02 / 31041 (or US 2004/051210)
• silanes or POSS carrying azo-dicarbonyl functional groups as described for example in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534.
• silanes bearing at least one thiol (SH) function (so-called mercaptosilanes) and / or of at least one blocked thiol function, as described by for example in patents or patent applications US 6849754, WO 99/09036, WO 2006/023815, WO 2007/098080.
• SH thiol
• the level of coupling agent is advantageously less than 20 phr. Its level is preferably between 0.5 and 12 phr, more preferably from 3 to 10 phr, in particular from 4 to 7 phr. This level is easily adjusted by those skilled in the art according to the level of inorganic filler used in the composition.
• the rubber compositions in accordance with the invention may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents as described above, or more generally, assisting agents for the implementation of the invention. in a known manner, by improving the dispersion of the filler in the rubber matrix and by lowering the viscosity of the compositions, to improve their ability to use in the green state, these agents being examples of hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
• hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
• the rubber compositions in accordance with the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tires, for example pigments, protective agents such as anti-ozone waxes, chemical antioxidants, anti-fatigue agents, anti-fatigue agents, reinforcing or plasticizing resins, acceptors (for example phenolic novolak resin) and methylene donors (for example HMT or H3M) as described for example in the WO application 02/10269, a crosslinking system based on either sulfur, or sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators, adhesion promoters such as cobalt base, plasticizing agents, preferably non-aromatic or very weakly aromatic selected from the group consisting of hu naphthenic, paraffinic, MES oils, TDAE oils, ethers plasticizers, ester plasticizers (for example glycerol trioleate), hydrocarbon resins
• the invention also relates to a method for preparing a rubber composition as described above.
• the polyimine compound can be incorporated, on an open tool of cylinder type (external mixer) or on closed tool of the internal mixer type, at any time in the process for the preparation of the rubber composition described below, including during the manufacture of natural rubber at its production site.
• composition is manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: (i) a first phase of work or thermomechanical mixing (so-called “non-productive” phase) at high temperature, up to 'at a maximum temperature between 130 0 C and 200 0 C, preferably between 145 ° C and 185 ° C, followed by (ii) a second phase of mechanical working (so-called “productive” phase) to a more low temperature, typically less than 110 0 C, for example between 40 0 C and 100 0 C, also called finishing phase, during which is incorporated the crosslinking system.
• crosslinking system is meant indifferently the crosslinking agents conventionally used with the inorganic fillers and vulcanizing agents conventionally used such as sulfur and vulcanization accelerators.
• the first phase is conducted in a single thermomechanical step during which is introduced into a suitable mixer such as an internal mixer, in a first time at a temperature between 60 0 C and 110 ° C., for example of the order of 80 ° C., or the diene elastomers, then in a second time, for example after about 30 seconds of mixing, the reinforcing filler, the polyimine compound at the low rate mentioned above. , any additional processing agents and other additives, with the exception of the crosslinking or vulcanization system.
• the total mixing time, in this non-productive phase is preferably between 2 and 6 minutes with a falling temperature of the order of 165 ° C.
• the vulcanization system is then incorporated at a temperature of between 20 ° C. and 50 ° C., for example of the order of 40 ° C., generally in an external mixer such as a cylinder mixer. ; everything is then mixed (productive phase) for a few minutes, for example between 2 and 6 minutes.
• the process according to the invention for preparing a rubber composition according to the invention comprises at least the following steps:
• thermomechanical working time (sometimes referred to as a "non-productive" phase) of the necessary basic constituents of the rubber composition, including the poly-imine compound (s) at the above-mentioned low level, with the exception of the crosslinking system, by incorporation of intimately, by kneading in one or more steps, to the elastomer matrix based on natural rubber, constituents of the composition, then
• the polyimine compound to be incorporated in the composition must be incorporated at a low level, that is to say a level of between 0 and 6 mmol. per 100g of elastomer.
• said variant comprises, prior to the completion of step (i) above, the steps of the conventional manufacture of natural rubber which comprises the addition of the poly compound imine corresponding to formulas 1 or 2.
• Another variant of the process according to the invention comprises, prior to carrying out step (i) above, a step of preparing a masterbatch based on natural rubber and the polyimine compound of formula 1 or 2.
• the final composition thus obtained can then be calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile usable as a semi-finished rubber product for the tire.
• the invention also relates to a tire which incorporates in at least one of its constituent elements a reinforced rubber composition according to the invention.
• the invention particularly relates to a semi-finished rubber product comprising a reinforced rubber composition according to the invention for these tires. Because of the reduced hysteresis which characterizes a reinforced rubber composition according to the invention with respect to the hysteresis of the composition free of polyimine compound, it will be noted that a tire whose tread comprises the composition according to the invention.
• the invention has improved hysteresis properties, in particular significantly reduces the initial hysteresis of the composition synonymous with a rolling resistance advantageously reduced.
• compositions are intended to mean compositions intended for the manufacture of crown reinforcement plies, carcass reinforcement plies, beads, protectors, underlays, rubber blocks and other internal gums, in particular gums. decoupling, intended to provide the connection or the interface between the aforementioned zones of the tires.
• the tires according to the invention are particularly intended for passenger vehicles, industrial vehicles chosen from the vans, "heavy goods vehicles” - ie, metro, buses, road transport vehicles (trucks, tractors, trailers), off-road vehicles. road, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
• HMDI cyclopentanone N, N'-dicyclopentylidenehexane-1,6-diamine
• a dean stark and a dropping funnel are introduced 50 g of 1,4-diaminocyclohexane (0.43 mol), 170 g of cyclohexanone. (1.7 mol) and 150 ml of methylcyclohexane.
• the reaction medium is sparged with nitrogen for 5 minutes at room temperature and then heated at reflux with a thermostatically controlled oil bath whose temperature is 160 ° C. After reflux for 7 hours, the reaction medium is cooled, then the excess reagents are removed by evaporation at 80 0 C under a pressure of 20 mbar. 64 g of a white solid are obtained.
• the natural rubber used to form the masterbatches (M ..., for example, MB, MC or MD) is a NR referenced TSR20.
• Step 1 3 passes of the natural rubber initially at room temperature;
• Step 2 addition of a given amount of polyimines in powder form
• Step 3 Making 12 passes so as to disperse the powder and to homogenize the sample.
• the added amounts of the different imines are identical in terms of the number of moles of imine functions.
• the purpose of the exemplary embodiment is to compare the properties of a composition according to the invention comprising a low-level polyimine compound and prepared according to the process according to the invention with another identical composition but not comprising any polyimine compound.
• the procedure for producing the compositions is the same for all the compositions tested.
• the example shows the improved properties (hysteresis) of a composition according to the invention when the reinforcing filler is 100% an organic filler such as carbon black.
• the compositions tested have the following formulation (expressed in phr: parts per hundred parts of elastomer):
• thermomechanical working step is carried out for 3 to 5 minutes, until a maximum temperature of about 165 ° C. falls.
• thermomechanical work time is thus achieved, it being specified that the average speed of the pallets during this first time is 70 rpm.
• the sulfur and sulphenamide are added at 40 ° C., while still mixing for a period of 3 to 4 minutes (second aforementioned mechanical working time).
• 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.
• compositions B, C, D and E according to the invention have a Mooney value "mixture" greater than that of the composition A based on a NR only worked on tool.
• the values of Delta G * and tan ( ⁇ ) max of the compositions B, C, D and E are lower than those of the composition A based on a NR only passed on tool.
• the masterbatches MB, MC, MD or ME comprising a polyimine according to the invention make it possible to improve the initial hysteretic properties relative to the natural rubber A passed on a tool without introduction of polyimine compound.
• compositions B, C, D and E according to the invention based on NR comprising a polyimine have crosslinked rubber properties which are improved over those of the composition A to NR base unmodified due to significantly reduced hysteresis.

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