EP1718698A1 - Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same - Google Patents

Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same

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Publication number
EP1718698A1
EP1718698A1 EP05731113A EP05731113A EP1718698A1 EP 1718698 A1 EP1718698 A1 EP 1718698A1 EP 05731113 A EP05731113 A EP 05731113A EP 05731113 A EP05731113 A EP 05731113A EP 1718698 A1 EP1718698 A1 EP 1718698A1
Authority
EP
European Patent Office
Prior art keywords
crosslinking
composition according
elastomer
chosen
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05731113A
Other languages
German (de)
French (fr)
Inventor
Laurent Gervat
Nicolas Garois
Philippe Sonntag
Adrian Verschave
Logan Bouchereau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR0401826A external-priority patent/FR2866651A1/en
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP1718698A1 publication Critical patent/EP1718698A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a crosslinked composition, to its manufacturing process and to its uses. It particularly describes a crosslinked composition comprising an elastomer and a triblock block copolymer, its production process based on crosslinking at high temperature and its uses.
  • the crosslinked composition of the invention finds its applications in the manufacture of certain articles such as seals and insulation linings as well as conduits for transferring fluids such as those used in the automotive industry, for example in braking circuits or cooling. Other applications such as the manufacture of belts (such as transmission belts), tires, sheaths of electric cables, shoe soles can use the compositions of the invention.
  • a particular case of the invention consists of such crosslinked compositions which can be transformed like thermoplastic materials.
  • thermoplastic elastomers based on polyolefins which have a structure constituted by a. polypropylene matrix no. cross-linked and cross-linked ethylene / propylene / diene terpoly-nodules (EPDM), so as to have at the temperature of use -which is lower than the melting point of the polypropylene- behavior similar to that of the elastomers after vulcanization , while their heating above this melting temperature makes it possible to use them as thermoplastic materials.
  • EPDM cross-linked and cross-linked ethylene / propylene / diene terpoly-nodules
  • EP 0840763B1 proposes a solution based on the use of a cross-linked elastomer with thermoplastic transformation obtained by crosslinking a mixture, designated below as "Végaprène ®" comprising a polyolefin based elastomer (octene / ethylene) obtained by metallocene catalysis and polyolefin grafted with maleic anhydride.
  • Végaprène ® a polyolefin based elastomer (octene / ethylene) obtained by metallocene catalysis and polyolefin grafted with maleic anhydride.
  • the first object of the invention is therefore a crosslinked composition comprising in parts by mass: 20 to 100 parts of at least one elastomer (I), 2 to 50 parts of at least one triblock block copolymer (II), and 0 100 parts of at least one thermoplastic polymer (III).
  • the elastomer (I) can be chosen from the group comprising natural rubbers (NR), synthetic rubbers (BR), elastomers with metallocene catalysis polymerization, poly (ethylene / propylene) ( EPR), poly (ethylene / propylene / diene) (EPDM), long chain polyacrylates such as polybutylacrylate or ethyl 2-hexylacrylate and fluorinated elastomers (FPM) such as tetrafluoroethylene copolymers and elastomeric silicones.
  • synthetic rubber is meant conjugated polydienes such as polybutadiene, polyisoprene and their block or random copolymers.
  • the term “elastomer polymerized by a metallocene catalyst” means any elastomer constituted by a homopolymer, a copolymer or a terpolymer the polymerization of which has been carried out using a metallocene catalyst such as poly (octene / ethylene) also called polyoctenes, which are available from DU PONT DOW Elastomers (DDE) under the trade name ENGAGE.
  • a metallocene catalyst such as poly (octene / ethylene) also called polyoctenes, which are available from DU PONT DOW Elastomers (DDE) under the trade name ENGAGE.
  • the triblock block copolymer (II) corresponds to the following general formula:
  • Block B is an elastomer which may belong to the family of polyolefins, polyacrylates, polyurethane polyethers such as polyoxyethylene or polyoxypropylene, nitrile elastomers.
  • the monomer used to synthesize the elastomeric block B can be an alkene such as isobutylene, an acrylate or a long chain methacrylate such as butyl acrylate or 2-ethylhexyl acrylate or a diene chosen from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-phenyl-l, 3 ⁇ butadiene.
  • B is advantageously chosen from poly (dienes), in particular poly (butadiene), poly (isoprene) and their random copolymers, or also from poly (dienes) partially or completely hydrogenated according to the usual techniques.
  • the polybutadienes those with the lowest glass transition temperature, Tg, are advantageously used, for example polybutadiene-1,4 of Tg (around -90 ° C.) lower than that of polybutadiene-1,2. (around 0 ° C).
  • the blocks B consist mainly of polybutadiene-1,4.
  • the Tg of B is less than 0 ° C and preferably less than -40 ° C.
  • Y and Y ′ can be obtained by the polymerization of at least one monomer chosen from the group containing styrene and its derivatives, short chain methacrylates such as methyl methacrylate.
  • Y ′ consists of methyl methacrylate monomers or contains at least 50% by mass of methyl methacrylate, preferably at least 70% by mass of methyl methacrylate.
  • the other monomers constituting this block can be acrylic monomers or no, be reactive or not.
  • reactive functions mention may be made of: oxirane functions, amino functions, anhydride functions, carboxylic acid functions.
  • the reactive monomer can be a hydrolyzable monomer leading to acids.
  • the other monomers which can constitute the block Y ′ non-limiting examples that may be mentioned are glycidyl methacrylate, tert-butyl methacrylate, glutarimide.
  • the block Y ′ contains imide functions preferably in proportion between 30 and 60 mol% of Y ′. These imide functions can be obtained by imidization.
  • 2 adjacent MMA functions are imidized.
  • the imidization is described for example in patents EP 275918, EP315149, EP315150, EP315151 and EP331052, the content of which is incorporated in the present application.
  • the composition of the invention can be prepared using a triblock copolymer II having a block Y 'already imidized or the imidization can be carried out during the mixing of components I, II and optionally III of the invention.
  • Advantageously M consists of polymethyl methacrylate (PMMA) syndiotactic at least 60%.
  • Y has a chemical composition different from Y ', as in the case of the examples below, it can be obtained by the polymerization of vinyl aromatic compounds such as for example styrene, ⁇ -methyl styrene, vinyltoluene, vinylpyridines .
  • Y is then designated by S.
  • the Tg of Y (or S) is advantageously greater than 23 ° C and preferably greater than 50 ° C.
  • the triblock copolymer, YB-Y ′, according to the invention is hereinafter designated by SBM.
  • the SBM has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
  • the SBM triblocks advantageously has the following composition expressed in mass fraction, the total being 100%: M: between. 10 and 80% and preferably between 15 and 70%. B: between 2 and 80% and preferably between 5 and 70%. S: between 10 and 88% and preferably between 5 and 85%.
  • the block copolymer (II) can contain at least one diblock SB in which the blocks S and B have the same properties as the blocks S and B of the triblock SBM. They consist of the same monomers and possibly comonomers as the S blocks and the B blocks of the SBM triblock.
  • the dibloc SB has a number-average molar mass which can be between 5000 g / mol and 500000 g / mol, preferably between 10000 and 200000 g / mol.
  • the diblock S ⁇ B advantageously consists of a mass fraction in B of between 5 and 95% and preferably between 15 and 85%.
  • the mixture of SB diblock and SBM triblocks is hereinafter designated SBM. This mixture advantageously comprises between 5 and 80% of SB diblock for respectively from 95 to 20% of SBM triblocks.
  • the thermoplastic polymer III is chosen, for example, from modified or unmodified polyolefins, polyamides, polyesters, thermoplastic polyurethanes, fluorinated polymers and chlorinated polymers such as polyvinyl chloride (PVC).
  • the polymer therm 'oplastique III is advantageously a functionalized polyolefin.
  • the thermoplastic polymer III is preferably a grafted polyolefin chosen from the group comprising polyethylenes, polypropylenes and poly (ethylene / pro ⁇ ylene) grafted with acrylic acid, maleic anhydride or glycidyl methacrylate.
  • the crosslinked composition according to the invention may also contain a polyacrylic elastomer such as a terpolymer of ethylene, acrylate and acrylic acid or a terpolymer of styrene, acrylonitrile and acrylate , which plays the role of anti-ultraviolet agent and film-forming agent and which makes it possible to improve the surface appearance of the composition when the latter is used by extrusion.
  • a polyacrylic elastomer is used, it is preferably used at a rate of 2 to 20 parts by mass per 100 parts by mass of the elastomer / triblock block copolymer mixture.
  • the composition of the invention may contain, in addition, a plasticizer whose presence makes it possible to increase its fluidity and, therefore, to facilitate its implementation, as well as to adjust the hardness of the products resulting from this implementation as a function of a desired hardness value.
  • this plasticizer is a paraffinic plasticizer of the type of those sold by the company TOTAL under the trade name PLAXENE or by the company EXXON under the trade name FLEXON, and is used in an amount of 5 to 120 parts by mass per 100 parts in mass of the elastomer / triblock copolymer and optionally grafted polyolefin mixture.
  • the composition can also contain fillers of the clear fillers type: silicas, carbonates, clays, chalk, kaolin, etc. or carbon blacks.
  • silicas, carbonates, clays, chalk, kaolin, etc. or carbon blacks The use of the latter has proved to be particularly advantageous since they make it possible not only to modulate certain mechanical properties of the composition in accordance with the invention such as the breaking strength or the tensile modules, but also to give it a excellent resistance to the action of ultraviolet.
  • fillers are present in the composition, they are advantageously present up to 5 to 100 parts by mass per 100 parts by mass of the elastomer / triblock copolymer and optionally grafted polyolefin mixture.
  • the crosslinked composition may also contain other adjuvants conventionally used in the polymer industry, such as, for example, antistatics, lubricants, antioxidants, coupling agents, dyes, processing agents or still adhesion promoters according to the properties that one wishes to give it provided, of course, that these adjuvants are compatible with each other.
  • adjuvants conventionally used in the polymer industry, such as, for example, antistatics, lubricants, antioxidants, coupling agents, dyes, processing agents or still adhesion promoters according to the properties that one wishes to give it provided, of course, that these adjuvants are compatible with each other.
  • the composition according to the invention is said to be "crosslinked” because its preparation involves crosslinking of the elastomer entering into its composition.
  • the composition according to the invention contains, before crosslinking, at least one crosslinking system comprising one or more crosslinking agents suitably chosen according to the nature of the polymers forming part of its composition and one or more crosslinking promoters whose function is to activate the kinetics of the reaction and to increase the crosslinking density.
  • this crosslinking system comprises, as crosslinking agent (s), one or more organic peroxides chosen from the group comprising dicumyl peroxide, 1,3-bis- (t-butyl peroxide).
  • the crosslinking system is a sulfur-based system which comprises, in addition to zinc oxide and / or stearic acid as crosslinking promoter (s), one or more sulfur donor accelerators such as 4,4-dithiomorpholine, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide or zinc dibutyldithiocarbamate, and, optionally, an anti-reversion agent such as 1,3-bis- (cistraconimido-methyl )benzene.
  • crosslinking promoter s
  • one or more sulfur donor accelerators such as 4,4-dithiomorpholine, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide or zinc dibutyldithiocarbamate
  • an anti-reversion agent such as 1,3-bis- (cistraconimido-methyl )benzene.
  • the crosslinking system comprises, as crosslinking agent, a phenolic resin chosen from reactive alkylated methyl-phenolformaldehyde resins and bromo-methyl-phenolformaldehyde resins, and as crosslinking promoter, a chlorinated polymer such as '' a chlorinated or chlorosulfonated polyethylene or a polychloroprene, optionally combined with zinc oxide and / or stearic acid.
  • a chlorinated polymer such as '' a chlorinated or chlorosulfonated polyethylene or a polychloroprene, optionally combined with zinc oxide and / or stearic acid.
  • the crosslinking agent (s) are preferably present in the formulation up to 1 to 10 parts by mass per 100 parts by mass of the elastomer / triblock copolymer and optionally grafted polyolefin blend, while the crosslinking promoter (s) are preferably present at a level of 0.5 to 12 parts by mass per 100 parts by mass of the mixture.
  • the sulfur donor accelerator or accelerators are, for their part, preferably present in the formulation at a level of 1 to 7 parts by mass per 100 parts by mass of the elastomeric mixture / triblock copolymer and optionally grafted polyolefin.
  • the crosslinking of the composition can be carried out by means of two crosslinking systems.
  • a crosslinking system based on sulfur and a crosslinking system based on organic peroxides or a crosslinking system based on a phenolic resin and a crosslinking system based on organic peroxides can be used together.
  • the compositions of the invention can be transformed by the techniques and materials used for the implementation of thermoplastic materials: thermoforming, injection molding, extrusion, forming ... In this particular case, the compositions of the invention are said to be "thermoplastic transformation".
  • the elastomer I consists of a homopolymer, a copolymer or a terpolymer, the polymerization of which was carried out using a metallocene catalyst and the polymer III is present.
  • Advantageously III is a functionalized polyolefin, preferably a grafted polyolefin. It can be chosen from grafted polyolefins as mentioned above. For example one can mixtures I and III known as "végaprène ®".
  • thermoplastic transformation compositions in accordance with the invention while having mechanical properties in terms of hardness, breaking strength and elongation at break equivalent to those of the previously mentioned thermoplastic elastomers of the prior art, have better remanence properties in compression and elongation than the latter. This advantage can be seen not only in the short term but also in the long term term in which the compositions in accordance with the invention show a less tendency to creep.
  • the present invention also relates to a process for the manufacture of a crosslinked composition as defined above, characterized in that it comprises the mixing of an elastomer and a triblock block copolymer in the optional presence of a polyolefin grafted, of a plasticizer, fillers and / or adjuvants, and the crosslinking of this mixture by a crosslinking system suitably chosen at an appropriate temperature.
  • a crosslinking system suitably chosen at an appropriate temperature.
  • the temperature at which the crosslinking is carried out is between 150 and 320 ° C.
  • the process in accordance with the invention comprises: a) mixing the elastomer, the triblock block copolymer and the crosslinking system in the presence, optionally, of the thermoplastic polymer, polyacrylic elastomer, plasticizer, fillers and / or adjuvants; b) heating this mixture to a temperature between 150 and 320 ° C, and c) keeping it at this temperature for a time between 1 and 15 minutes.
  • This process can be implemented in an internal mixer or, as a variant, in a twin-screw extruder or a co-kneader of the BUSS type.
  • the resulting mass is, as the case may be, calendered or extruded, then cooled and subjected to granulation.
  • the granules thus obtained are ready to be processed - by heating these granules into sheets, plates, profiles, tubes or other desired products.
  • the present invention also relates to the use of a crosslinked composition as defined above for the manufacture of joints and insulating and / or sealing gaskets as used for thermal, sound and / or waterproofing and humidity, especially in the building and by the automotive industry (door fittings for example).
  • the present invention further relates to the use of such a composition in the manufacture of conduits, tubes, pipes, tubing, fittings or the like for the transfer of fluids.
  • NR / BR compositions for dynamic applications stops, motor support, 2.
  • Vegaprene 2 compositions for application of the cable, pipe coating type It goes without saying, however, that these examples are given solely by way of illustrations of the subject of the invention of which they do not in any way constitute a limitation.
  • Tables 3 and 4 show that there is an improvement in the elongation and the Delft tear which is important for the positioning and the resistance of the part.
  • Table 5 Typical formulation Vegaprene 2

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Organic Insulating Materials (AREA)

Abstract

The invention relates to a cross-linked composition comprising at least one elastomer and at least one triblock sequenced copolymer. The invention also relates to a method for obtaining one such composition, based on a system and a suitably selected cross-linking temperature. According to a preferred embodiment of the invention, the cross-linked composition can be transformed as a thermoplastic material. The inventive composition can be used in various applications, especially for producing conduits for the transfer of fluids, seals and insulation linings.

Description

COMPOSITION RETICULEE COMPRENANT UN COPOLYMERE SEQUENCE TRIBLOCS, SON PROCÉDÉ D'OBTENTION ET SES UTILISATIONSCROSSLINKED COMPOSITION COMPRISING A TRIBLOCK BLOCK COPOLYMER, PROCESS FOR OBTAINING SAME AND USES THEREOF
La présente invention se rapporte à une composition réticulée, à son procédé de fabrication et à ses utilisations. Elle décrit particulièrement une composition réticulée comprenant un élastomère et un copolymère séquence triblocs, son procédé d'obtention basé sur une réticulation à haute température et ses utilisations. La composition réticulée de l'invention trouve ses applications dans la fabrication de certains articles tels que les joints et garnitures d'isolation ainsi que les conduits pour transfert des fluides comme ceux utilisés dans l'industrie automobile, par exemple dans les circuits de freinage ou de refroidissement. D'autres applications telles que la fabrication de courroies (comme des courroies de transmission), de pneus, de gaines de câbles électriques, de semelles de chaussures peuvent faire appel aux compositions de l'invention. Un cas particulier de l'invention consiste en de telles compositions réticulées et pouvant être transformées comme les matériaux thermoplastiques. En effet, pour certaines applications (joints et garnitures d'isolation ou conduit de transfert de fluide) il est souhaitable de disposer de matériaux qui, tout en présentant des propriétés semblables à celles des élastomères et notamment, une aptitude à supporter des déformations importantes sans rupture et une capacité à retrouver leur géométrie initiale après des sollicitations du type allongement ou compression, même répétées, ainsi qu'une bonne tenue à la chaleur, aux agents chimiques et aux intempéries, peuvent être mis en oeuvre par les techniques et le matériel qu'utilisent les transformateurs de matières thermoplastiques, et ce, principalement, pour permettre le recyclage de ces articles ainsi que celui des déchets produits au cours de leur fabrication, recyclage que n'autorise pas l'utilisation d'élastomères. Aussi, a-t-on proposé dans US-A-4 130 535 des "élastomères thermoplastiques" à base de polyoléfines qui présentent une structure constituée par une . matrice de polypropylène non . réticulée et des nodules -de terpoly-mère éthylène/propylène/diène (EPDM) réticulés, de manière à présenter à la température d'utilisation -qui est inférieure à la température de fusion du polypropylène- un comportement analogue à celui des élastomères après vulcanisation, tandis que leur chauffage au-dessus de cette température de fusion permet de les mettre en oeuvre comme des matières thermoplastiques. Si ces matériaux présentent effectivement un certain nombre de propriétés équivalentes à celles des élastomères, ils montrent toutefois une déformation rémanente à l'allongement importante (supérieure à 50%) à des températures supérieures à 100°C, ce qui rend leur utilisation peu appropriée à la fabrication d'articles destinés à être utilisés dans des zones où régnent des températures de plus de 100°C comme peuvent l'être les joints et garnitures d'isolation et/ou d'étanchéité ou encore les conduits, tuyaux, tubes et analogues prévus pour assurer le transfert de fluides dans le compartiment moteur d'une automobile. Pour résoudre ce problème EP 0840763B1 propose une solution basée sur l'utilisation d'un élastomère réticulé à transformation thermoplastique obtenu par la réticulation d'un mélange, désigné plus loin par « Végaprène® », comprenant un élastomère à base de poly(octène/éthylène) obtenu par catalyse métallocène et polyoléfine greffée anhydride maléique. Bien que cette solution soit satisfaisante, elle reste néanmoins limitée à certaines applications. En effet, les propriétés des mélanges sont en général différentes de celles prévues par une simple interpolation linéaire de celles des constituants pris séparément (élastomères et plastiques). Des effets de synergie peuvent parfois être présents mais il existe d'autres cas où les propriétés sont légèrement inférieures. Ceci peut se relier à la morphologie des différentes phases, à la distribution des charges et plastifiants, à la nature des interfaces ou à la distribution des ponts de vulcanisation dans les différentes phases. Pour pallier ces phénomènes on fait généralement appel à des agents compatibilisants ou à des co-agents qui sont coûteux et difficiles à incorporer dans les mélanges. En particulier dans le cas des propriétés de résistance à des sollicitations répétées le comportement en fatigue des composés est primordial. Ceci peut être obtenu à l'aide de co-agents tels le méthacrylate de zinc. Toutefois en raison de la polarité de ce composé celui-ci est difficile à disperser dans les mélanges. De plus sa forte réactivité avec le métal à haute température conduit à des mélanges qui adhèrent aux outils de mélangeage. Il est par conséquent peu utilisé. Une autre propriété intéressante peut être la résistance à un allongement élevé. Cette caractéristique est difficile à obtenir avec les mélanges décrits dans EP 0840763 Bl. Enfin dans certains cas l'amélioration de la Déformation Rémanente à la Compression, désignée généralement par DRC, obtenue par l'application du procédé décrit dans EP 0840763 Bl peut se révéler insuffisante. Pour résoudre les problèmes décrits précédemment et bien d'autres la demanderesse a trouvé une solution basée sur une composition réticulée comprenant au moins un élastomère et au moins un copolymère séquence triblocs et éventuellement un polymère thermoplastique. La solution trouvée par la demanderesse permet de résoudre les problèmes cités précédemment sans modifier de manière néfaste les autres caractéristiques mécaniques des mélanges (propriétés dynamiques, dissipation, dureté, rebond---). Le mélange est facile à disperser suivant la méthode décrite dans la présente invention. De plus il présente l'avantage de ne pas adhérer aux équipements. Le premier objet de l'invention est donc une composition réticulée comprenant en parties en masse : 20 à 100 parties d'au moins un élastomère (I), 2 à 50 parties d'au moins un copolymère séquence triblocs (II), et 0 à 100 parties d'au moins un polymère thermoplastique (III). Au sens de la présente invention, l'élastomère (I) peut être choisi dans le groupe comprenant les caoutchoucs naturels (NR), les caoutchoucs synthétiques (BR), les élastomères à polymérisation par catalyse métallocène, les poly(ethylène/propylène)(EPR), les poly(éthylène/propylène/diène) (EPDM), les polyacrylates à chaîne longue tels que le polyacrylate de butyle ou le polyacrylate d'éthyle 2-héxyle et les élastomères fluorés (FPM) comme les copolymères à base de tetrafluoroéthylène et les silicones élastomères. Par caoutchouc synthétique (BR) on entend les polydiènes conjuguées telles que le polybutadiène, le polyisoprène et leurs copolymères séquences ou statistiques. Au sens de la présente invention, on entend par élastomère à polymérisation par un catalyseur métallocène, tout élastomère constitué par un homopolymère, un copolymère ou un terpolymère dont la polymérisation a été réalisée au moyen d'un catalyseur métallocène tels que les poly(octène/éthylène) appelés encore polyoctènes, qui sont disponibles auprès de la Société DU PONT DOW Elastomers (DDE) sous la dénomination commerciale ENGAGE. Selon l'invention le copolymère séquence triblocs (II) répond à la formule générale suivante :The present invention relates to a crosslinked composition, to its manufacturing process and to its uses. It particularly describes a crosslinked composition comprising an elastomer and a triblock block copolymer, its production process based on crosslinking at high temperature and its uses. The crosslinked composition of the invention finds its applications in the manufacture of certain articles such as seals and insulation linings as well as conduits for transferring fluids such as those used in the automotive industry, for example in braking circuits or cooling. Other applications such as the manufacture of belts (such as transmission belts), tires, sheaths of electric cables, shoe soles can use the compositions of the invention. A particular case of the invention consists of such crosslinked compositions which can be transformed like thermoplastic materials. Indeed, for certain applications (seals and insulation linings or fluid transfer duct) it is desirable to have materials which, while having properties similar to those of elastomers and in particular, an ability to withstand significant deformations without rupture and an ability to recover their initial geometry after stresses of the elongation or compression type, even repeated, as well as good resistance to heat, chemical agents and weathering, can be implemented by the techniques and the material which '' use transformers of thermoplastics, and this, mainly, to allow the recycling of these items as well as that of the waste produced during their manufacture, recycling that does not allow the use of elastomers. Also, has it been proposed in US-A-4 130 535 "thermoplastic elastomers" based on polyolefins which have a structure constituted by a. polypropylene matrix no. cross-linked and cross-linked ethylene / propylene / diene terpoly-nodules (EPDM), so as to have at the temperature of use -which is lower than the melting point of the polypropylene- behavior similar to that of the elastomers after vulcanization , while their heating above this melting temperature makes it possible to use them as thermoplastic materials. While these materials do indeed exhibit a number of properties equivalent to those of elastomers, they nonetheless show a significant non-elongated deformation (greater than 50%) at temperatures above 100 ° C., which makes their use unsuitable for the manufacture of articles intended to be used in zones where temperatures prevail of more than 100 ° C as can be the joints and packing of insulation and / or sealing or even conduits, pipes, tubes and the like designed to transfer fluids into the engine compartment of an automobile. To resolve this problem EP 0840763B1 proposes a solution based on the use of a cross-linked elastomer with thermoplastic transformation obtained by crosslinking a mixture, designated below as "Végaprène ®" comprising a polyolefin based elastomer (octene / ethylene) obtained by metallocene catalysis and polyolefin grafted with maleic anhydride. Although this solution is satisfactory, it nevertheless remains limited to certain applications. In fact, the properties of the mixtures are generally different from those predicted by a simple linear interpolation from those of the constituents taken separately (elastomers and plastics). Synergistic effects can sometimes be present but there are other cases where the properties are slightly lower. This can relate to the morphology of the different phases, to the distribution of the charges and plasticizers, to the nature of the interfaces or to the distribution of the vulcanization bridges in the different phases. To overcome these phenomena, use is generally made of compatibilizing agents or co-agents which are expensive and difficult to incorporate into mixtures. In particular in the case of properties of resistance to repeated stresses, the fatigue behavior of the compounds is essential. This can be achieved using co-agents such as zinc methacrylate. However, due to the polarity of this compound, it is difficult to disperse in the mixtures. In addition, its high reactivity with the metal at high temperature leads to mixtures which adhere to the mixing tools. It is therefore little used. Another interesting property may be the resistance to high elongation. This characteristic is difficult to obtain with the mixtures described in EP 0840763 B1. Finally, in certain cases the improvement in the Remanent Deformation to Compression, generally designated by DRC, obtained by applying the method described in EP 0840763 B1 may prove to be insufficient. To solve the problems described above and many others, the applicant has found a solution based on a crosslinked composition comprising at least one elastomer and at least one triblock block copolymer and optionally a thermoplastic polymer. The solution found by the applicant makes it possible to solve the problems cited above without adversely modifying the other mechanical characteristics of the mixtures (dynamic properties, dissipation, hardness, rebound ---). The mixture is easy to disperse according to the method described in the present invention. In addition, it has the advantage of not adhering to the equipment. The first object of the invention is therefore a crosslinked composition comprising in parts by mass: 20 to 100 parts of at least one elastomer (I), 2 to 50 parts of at least one triblock block copolymer (II), and 0 100 parts of at least one thermoplastic polymer (III). Within the meaning of the present invention, the elastomer (I) can be chosen from the group comprising natural rubbers (NR), synthetic rubbers (BR), elastomers with metallocene catalysis polymerization, poly (ethylene / propylene) ( EPR), poly (ethylene / propylene / diene) (EPDM), long chain polyacrylates such as polybutylacrylate or ethyl 2-hexylacrylate and fluorinated elastomers (FPM) such as tetrafluoroethylene copolymers and elastomeric silicones. By synthetic rubber (BR) is meant conjugated polydienes such as polybutadiene, polyisoprene and their block or random copolymers. For the purposes of the present invention, the term “elastomer polymerized by a metallocene catalyst” means any elastomer constituted by a homopolymer, a copolymer or a terpolymer the polymerization of which has been carried out using a metallocene catalyst such as poly (octene / ethylene) also called polyoctenes, which are available from DU PONT DOW Elastomers (DDE) under the trade name ENGAGE. According to the invention, the triblock block copolymer (II) corresponds to the following general formula:
Y-B-Y' dans laquelle B est un bloc à caractère élastomère, Y et Y' sont thermodynamiquement incompatibles avec le bloc B. Ils peuvent être de composition chimique identique ou non et au moins l'un d'eux est constitué majoritairement de monomères méthacryliques. Le bloc B est un élastomère pouvant appartenir à la famille des polyoléfines, polyacrylates, polyuréthannes polyethers tels que polyoxyethylène ou polyoxypropylène, élastomères nitriles. Notamment le monomère utilisé pour synthétiser le bloc B élastomérique peut être un alcène tel que l'isobutylène, un acrylate ou un méthacrylate à chaîne longue tel que l'acrylate de butyle ou l'acrylate de 2-éthyl-hexyle ou un diène choisi parmi le butadiène, l'isoprène, le 2,3-diméthyl- 1,3-butadiène, le 1,3-pentadiène, le 2-phényl-l,3~butadiène. B est choisi avantageusement parmi les poly(diènes) notamment poly(butadiène), poly(isoprène) et leurs copolymères statistiques, ou encore parmi les poly(diènes) partiellement ou totalement hydrogénés selon les techniques habituelles. Parmi les polybutadiènes on utilise avantageusement ceux dont la température de transition vitreuse, Tg, est la plus faible, par exemple le polybutadiène-1,4 de Tg (vers -90°C) inférieure à celle du polybutadiène-1,2. (vers 0°C). De préférence les blocs B sont constitués en majorité de polybutadiène-1,4. Avantageusement la Tg de B est inférieure à 0°C et de préférence inférieure à -40°C. Y et Y' peuvent être obtenus par la polymérisation d'au moins un monomère choisi dans le groupe contenant le styrène et ses dérivés, les méthacrylates à chaîne courte tels que le méthacrylate de méthyle. Préférentiellement Y' désigné alors par M est constitué de monomères de méthacrylate de méthyle ou contient au moins 50% en masse de méthacrylate de méthyle, de préférence au moins 70% en masse de méthacrylate de méthyle. Les autres monomères constituant ce bloc peuvent être des monomères acryliques ou non, être réactifs ou non. A titre d'exemples non limitatifs de fonctions réactives on peut citer : les fonctions oxiranes, les fonctions aminés, les fonctions anhydrides, les fonctions acides carboxyliques. Le monomère réactif peut être un monomère hydrolysable conduisant à des acides. Parmi les autres monomères pouvant constituer le bloc Y' on peut citer à titre d'exemples non limitatifs le méthacrylate de glycidyle, le méthacrylate de tertio-butyle, le glutarimide. Selon une forme avantageuse le bloc Y' contient des fonctions imides de préférence en proportion entre 30 et 60% molaire de Y'. Ces fonctions imides peuvent être obtenues par imidisation. Avantageusement on effectue l'imidisation de 2 fonctions MMA adjacentes. L'imidisation est décrite par exemple dans les brevets EP 275918, EP315149, EP315150, EP315151 et EP331052 dont le contenu est incorporé dans la présente demande. On peut préparer la composition de l'invention en utilisant un copolymère tribloc II ayant un bloc Y' déjà imidisé ou effectuer l'imidisation au cours du mélange des composants I, II et éventuellement III de l'invention. Avantageusement M est constitué de polyméthacrylate de méthyle (PMMA) syndiotactique à au moins 60%. Lorsque Y est de composition chimique différente de Y', comme dans le cas des exemples ci-dessous, il peut être obtenu par la polymérisation de composés vinylaromatiques tels que par exemple le styrène, l'a- méthyl styrène, le vinyltoluène, les vinylpyridines. Y est alors désigné par S. La Tg de Y (ou S) est avantageusement supérieure à 23°C et de préférence supérieure à 50°C. Le copolymère triblocs, Y-B-Y', selon l'invention est désigné par la suite par S-B-M.. Selon l'invention le S-B-M a une masse molaire moyenne en nombre qui peut être comprise entre 10000 g/mol et 500000 g/mol, de préférence comprise entre 20000 et 200000 g/mol. Le triblocs S-B-M avantageusement a la composition suivante exprimée en fraction massique, le total étant 100% : M : entre. 10 et 80% et de préférence entre 15 et 70%. B : entre 2 et 80% et de préférence entre 5 et 70%. S : entre 10 et 88% et de préférence entre 5 et 85%. Selon l'invention le copolymère séquence (II) peut contenir au moins un dibloc S-B dans lequel les blocs S et B ont les mêmes propriétés que les blocs S et B du triblocs S-B-M. Ils sont constitués des mêmes monomères et éventuellement comonomères que les blocs S et les blocs B du triblocs S-B-M. Le dibloc S-B a une masse molaire moyenne en nombre qui peut être comprise entre 5000 g/mol et 500000 g/mol, de préférence comprise entre 10000 et 200000 g/mol. Le dibloc S~B est avantageusement constitué d'une fraction massique en B comprise entre 5 et 95% et de préférence entre 15 et 85%. Le mélange de dibloc S-B et de triblocs S-B-M est désigné ci-après SBM. Ce mélange comprend avantageusement entre 5 et 80% de dibloc S-B pour respectivement de 95 à 20% de triblocs S-B-M. Un avantage de ces compositions à blocs, SBM, est qu'il n'est pas nécessaire de purifier le S-B-M à l'issue de sa synthèse. Le polymère thermoplastique III est choisi par exemple parmi les polyoléfines modifiées ou non modifiées, les polyamides, les polyesters, les polyuréthanes thermoplastiques, les polymères fluorés et les polymères chlorés comme le chlorure de polyvinyle (PVC). Le polymère therm'oplastique III est avantageusement une polyoléfine fonctionnalisée. Le polymère thermoplastique III est de préférence une polyoléfine greffée choisie dans le groupe comprenant les polyéthylènes, les polypropylènes et les poly(éthylène/proρylène) greffés d'acide acrylique, d'anhydride maléique ou de méthacrylate de glycidyle. De manière avantageuse, la composition réticulée conforme à l'invention peut, également, renfermer un élastomère polyacrylique tel qu'un terpolymère d'éthylène, d'acrylate et d'acide acrylique ou un terpolymère de styrène, d'acrylonitrile et d'acrylate, qui joue le rôle d'agent anti-ultraviolets et d'agent filmogène et qui permet d'améliorer l'aspect de surface de la composition lorsque celle-ci est mise en oeuvre par extrusion. Lorsqu'un tel élastomère polyacrylique est utilisé, il l'est de préférence à raison de 2 à 20 parties en masse pour 100 parties en masse du mélange élastomère / copolymère séquence triblocs. De manière également avantageuse, la composition de l'invention peut contenir, de plus, un plastifiant dont la présence permet d'augmenter sa fluidité et, partant, de faciliter sa mise en oeuvre, ainsi que d'ajuster la dureté des produits issus de cette mise en oeuvre en fonction d'une valeur de dureté recherchée. De préférence, ce plastifiant est un plastifiant paraffinique du type de ceux commercialisés par la Société TOTAL sous la dénomination commerciale PLAXENE ou par la Société EXXON sous la dénomination commerciale FLEXON, et est utilisé à raison de 5 à 120 parties en masse pour 100 parties en masse du mélange élastomère/copolymère triblocs et éventuellement polyoléfine greffée.YBY 'in which B is an elastomeric block, Y and Y' are thermodynamically incompatible with block B. They may have the same chemical composition or not and at least one of them consists mainly of methacrylic monomers. Block B is an elastomer which may belong to the family of polyolefins, polyacrylates, polyurethane polyethers such as polyoxyethylene or polyoxypropylene, nitrile elastomers. In particular, the monomer used to synthesize the elastomeric block B can be an alkene such as isobutylene, an acrylate or a long chain methacrylate such as butyl acrylate or 2-ethylhexyl acrylate or a diene chosen from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-phenyl-l, 3 ~ butadiene. B is advantageously chosen from poly (dienes), in particular poly (butadiene), poly (isoprene) and their random copolymers, or also from poly (dienes) partially or completely hydrogenated according to the usual techniques. Among the polybutadienes, those with the lowest glass transition temperature, Tg, are advantageously used, for example polybutadiene-1,4 of Tg (around -90 ° C.) lower than that of polybutadiene-1,2. (around 0 ° C). Preferably, the blocks B consist mainly of polybutadiene-1,4. Advantageously, the Tg of B is less than 0 ° C and preferably less than -40 ° C. Y and Y ′ can be obtained by the polymerization of at least one monomer chosen from the group containing styrene and its derivatives, short chain methacrylates such as methyl methacrylate. Preferably Y ′, then designated by M, consists of methyl methacrylate monomers or contains at least 50% by mass of methyl methacrylate, preferably at least 70% by mass of methyl methacrylate. The other monomers constituting this block can be acrylic monomers or no, be reactive or not. By way of nonlimiting examples of reactive functions, mention may be made of: oxirane functions, amino functions, anhydride functions, carboxylic acid functions. The reactive monomer can be a hydrolyzable monomer leading to acids. Among the other monomers which can constitute the block Y ′, non-limiting examples that may be mentioned are glycidyl methacrylate, tert-butyl methacrylate, glutarimide. According to an advantageous form, the block Y ′ contains imide functions preferably in proportion between 30 and 60 mol% of Y ′. These imide functions can be obtained by imidization. Advantageously, 2 adjacent MMA functions are imidized. The imidization is described for example in patents EP 275918, EP315149, EP315150, EP315151 and EP331052, the content of which is incorporated in the present application. The composition of the invention can be prepared using a triblock copolymer II having a block Y 'already imidized or the imidization can be carried out during the mixing of components I, II and optionally III of the invention. Advantageously M consists of polymethyl methacrylate (PMMA) syndiotactic at least 60%. When Y has a chemical composition different from Y ', as in the case of the examples below, it can be obtained by the polymerization of vinyl aromatic compounds such as for example styrene, α-methyl styrene, vinyltoluene, vinylpyridines . Y is then designated by S. The Tg of Y (or S) is advantageously greater than 23 ° C and preferably greater than 50 ° C. The triblock copolymer, YB-Y ′, according to the invention is hereinafter designated by SBM. According to the invention, the SBM has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol. The SBM triblocks advantageously has the following composition expressed in mass fraction, the total being 100%: M: between. 10 and 80% and preferably between 15 and 70%. B: between 2 and 80% and preferably between 5 and 70%. S: between 10 and 88% and preferably between 5 and 85%. According to the invention, the block copolymer (II) can contain at least one diblock SB in which the blocks S and B have the same properties as the blocks S and B of the triblock SBM. They consist of the same monomers and possibly comonomers as the S blocks and the B blocks of the SBM triblock. The dibloc SB has a number-average molar mass which can be between 5000 g / mol and 500000 g / mol, preferably between 10000 and 200000 g / mol. The diblock S ~ B advantageously consists of a mass fraction in B of between 5 and 95% and preferably between 15 and 85%. The mixture of SB diblock and SBM triblocks is hereinafter designated SBM. This mixture advantageously comprises between 5 and 80% of SB diblock for respectively from 95 to 20% of SBM triblocks. An advantage of these block compositions, SBM, is that it is not necessary to purify the SBM after its synthesis. The thermoplastic polymer III is chosen, for example, from modified or unmodified polyolefins, polyamides, polyesters, thermoplastic polyurethanes, fluorinated polymers and chlorinated polymers such as polyvinyl chloride (PVC). The polymer therm 'oplastique III is advantageously a functionalized polyolefin. The thermoplastic polymer III is preferably a grafted polyolefin chosen from the group comprising polyethylenes, polypropylenes and poly (ethylene / proρylene) grafted with acrylic acid, maleic anhydride or glycidyl methacrylate. Advantageously, the crosslinked composition according to the invention may also contain a polyacrylic elastomer such as a terpolymer of ethylene, acrylate and acrylic acid or a terpolymer of styrene, acrylonitrile and acrylate , which plays the role of anti-ultraviolet agent and film-forming agent and which makes it possible to improve the surface appearance of the composition when the latter is used by extrusion. When such a polyacrylic elastomer is used, it is preferably used at a rate of 2 to 20 parts by mass per 100 parts by mass of the elastomer / triblock block copolymer mixture. Also advantageously, the composition of the invention may contain, in addition, a plasticizer whose presence makes it possible to increase its fluidity and, therefore, to facilitate its implementation, as well as to adjust the hardness of the products resulting from this implementation as a function of a desired hardness value. Preferably, this plasticizer is a paraffinic plasticizer of the type of those sold by the company TOTAL under the trade name PLAXENE or by the company EXXON under the trade name FLEXON, and is used in an amount of 5 to 120 parts by mass per 100 parts in mass of the elastomer / triblock copolymer and optionally grafted polyolefin mixture.
Toutefois, d'autres plastifiants tels qu'un polyalkylbenzène peuvent également convenir. La composition peut renfermer, aussi, des charges du type charges claires : silices, carbonates, argiles, craie, kaolin, etc ou noirs de carbone. L'utilisation de ces derniers s'est révélée particulièrement avantageuse car ils permettent, non seulement de moduler certaines propriétés mécaniques de la composition conforme à l'invention telles que la résistance à la rupture ou les modules de traction, mais aussi de lui conférer une excellente résistance à l'action des ultraviolets. Lorsque de telles charges sont présentes dans la composition, elles le sont avantageusement à hauteur de 5 à 100 parties en masse pour 100 parties en masse du mélange élastomère/copolymère triblocs et éventuellement polyoléfine greffée. La composition réticulée peut contenir, en outre, d'autres adjuvants classiquement employés dans l'industrie des polymères comme, par exemple, des antistatiques, des lubrifiants, des antioxydants, des agents de couplage, des colorants, des agents de mise en oeuvre ou encore des promoteurs d'adhérence selon les propriétés que l'on souhaite lui donner pour autant, bien entendu, que ces adjuvants soient compatibles entre eux. La composition conforme à l'invention est dite "réticulée" en raison de ce que sa préparation implique une réticulation de l' élastomère entrant dans sa composition. De ce fait, la composition conforme à l'invention contient, avant réticulation, au moins un système de réticulation comprenant un ou plusieurs agents de réticulation convenablement choisis selon la nature des polymères entrant dans sa constitution et un ou plusieurs promoteurs de réticulation dont la fonction est d'activer la cinétique de la réaction et d'augmenter la densité de réticulation. Selon une disposition préférée de l'invention, ce système de réticulation comprend comme agent(s) de réticulation, un ou plusieurs peroxydes organiques choisis parmi le groupe comprenant le peroxyde de dicumyle, le peroxyde de 1,3- bis-(t-butyl-isopropyl)-benzène, le peroxyde de 2,5-diméthyl-2,5-bis-t- butylhexane et le l,l-bis-( t-butyl)-3,3,5-triméthylcyclohexane, et comme promoteur(s) de réticulation, un ou plusieurs composés choisis parmi le groupe comprenant l'oxyde de zinc, l'acide stéarique, le N,N-m-phénylène-dimaléimide, les cyanurates de triallyle ou de triisoallyle, les méthacrylates (comme les méthacrylates de tétrahydrofurfuryle ou de 2-phénoxyéthyle), les diméthacrylates (comme les diméthacrylates d'éthylène glycol, de tétraéthylène glycol, de 1,4- butanediol ou de zinc), les triméthacrylates (comme le triméthacrylate de triméthylolpropane) et les diacrylates (comme le diacrylate de zinc). Selon une autre disposition préférée de l'invention, le système de réticulation est un système basé sur le soufre qui comprend, outre de l'oxyde de zinc et/ou de l'acide stéarique comme promoteur(s) de réticulation, un ou plusieurs accélérateurs donneurs de soufre tels que la 4,4- dithiomorpholine, le disulfure de tétraméthylthiurame, le tétrasulfure de dipentaméthylènethiurame ou le dibutyldithiocarbamate de zinc, et, éventuellement, un agent anti- réversion tel que le l,3-bis-(cistraconimido-méthyl)benzène. Selon une disposition particulièrement préférée de l'Invention, le système de réticulation comprend comme agent de réticulation, une résine phénolique choisie parmi les résines méthyl- phénolformaldéhyde et bromo-méthyl-phénolformaldéhyde alkylées réactives, et comme promoteur de réticulation, un polymère chloré tel qu'un polyéthylène chloré ou chlorosulfoné ou un polychloroprène, éventuellement associé à de l'oxyde de zinc et/ou de l'acide stéarique. En effet, ce dernier système de réticulation permet d'obtenir des élastomères qui, outre de présenter des propriétés mécaniques- et de rémanence à l'allongement et à la compression extrêmement satisfaisantes, se caractérisent par un bel aspect de surface. Dans tous les cas, le ou les agents de réticulation sont, de préférence, présents dans la formulation à hauteur de 1 à 10 parties en masse pour 100 parties en masse du mélange élastomère/copolymère triblocs et éventuellement polyoléfine greffée, tandis que le ou les promoteurs de réticulation sont, de préférence, présents à hauteur de 0,5 à 12 parties en masse pour 100 parties en masse du mélange. Lorsque le système de vulcanisation est un système à base de soufre, le ou les accélérateurs donneurs de soufre sont, quant à eux, de préférence présents dans la formulation à hauteur de 1 à 7 parties en masse pour 100 parties en masse du mélange élastomère/copolymère triblocs et éventuellement polyoléfine greffée.However, other plasticizers such as polyalkylbenzene may also be suitable. The composition can also contain fillers of the clear fillers type: silicas, carbonates, clays, chalk, kaolin, etc. or carbon blacks. The use of the latter has proved to be particularly advantageous since they make it possible not only to modulate certain mechanical properties of the composition in accordance with the invention such as the breaking strength or the tensile modules, but also to give it a excellent resistance to the action of ultraviolet. When such fillers are present in the composition, they are advantageously present up to 5 to 100 parts by mass per 100 parts by mass of the elastomer / triblock copolymer and optionally grafted polyolefin mixture. The crosslinked composition may also contain other adjuvants conventionally used in the polymer industry, such as, for example, antistatics, lubricants, antioxidants, coupling agents, dyes, processing agents or still adhesion promoters according to the properties that one wishes to give it provided, of course, that these adjuvants are compatible with each other. The composition according to the invention is said to be "crosslinked" because its preparation involves crosslinking of the elastomer entering into its composition. Therefore, the composition according to the invention contains, before crosslinking, at least one crosslinking system comprising one or more crosslinking agents suitably chosen according to the nature of the polymers forming part of its composition and one or more crosslinking promoters whose function is to activate the kinetics of the reaction and to increase the crosslinking density. According to a preferred arrangement of the invention, this crosslinking system comprises, as crosslinking agent (s), one or more organic peroxides chosen from the group comprising dicumyl peroxide, 1,3-bis- (t-butyl peroxide). -isopropyl) -benzene, 2,5-dimethyl-2,5-bis-t-butylhexane peroxide and 1,1-bis- (t-butyl) -3,3,5-trimethylcyclohexane, and as promoter ( s) of crosslinking, one or more compounds chosen from the group comprising zinc oxide, stearic acid, N, Nm-phenylene-dimaleimide, triallyl or triisoallyl cyanurates, methacrylates (such as tetrahydrofurfuryl methacrylates or 2-phenoxyethyl), dimethacrylates (such as ethylene glycol, tetraethylene glycol, 1,4-butanediol or zinc dimethacrylates), trimethacrylates (such as trimethylolpropane trimethacrylate) and diacrylates (such as diacrylate zinc). According to another preferred arrangement of the invention, the crosslinking system is a sulfur-based system which comprises, in addition to zinc oxide and / or stearic acid as crosslinking promoter (s), one or more sulfur donor accelerators such as 4,4-dithiomorpholine, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide or zinc dibutyldithiocarbamate, and, optionally, an anti-reversion agent such as 1,3-bis- (cistraconimido-methyl )benzene. According to a particularly preferred arrangement of the invention, the crosslinking system comprises, as crosslinking agent, a phenolic resin chosen from reactive alkylated methyl-phenolformaldehyde resins and bromo-methyl-phenolformaldehyde resins, and as crosslinking promoter, a chlorinated polymer such as '' a chlorinated or chlorosulfonated polyethylene or a polychloroprene, optionally combined with zinc oxide and / or stearic acid. Indeed, this latter crosslinking system makes it possible to obtain elastomers which, apart from having extremely satisfactory mechanical properties and remanence to elongation and to compression, are characterized by a beautiful surface appearance. In all cases, the crosslinking agent (s) are preferably present in the formulation up to 1 to 10 parts by mass per 100 parts by mass of the elastomer / triblock copolymer and optionally grafted polyolefin blend, while the crosslinking promoter (s) are preferably present at a level of 0.5 to 12 parts by mass per 100 parts by mass of the mixture. When the vulcanization system is a sulfur-based system, the sulfur donor accelerator or accelerators are, for their part, preferably present in the formulation at a level of 1 to 7 parts by mass per 100 parts by mass of the elastomeric mixture / triblock copolymer and optionally grafted polyolefin.
Conformément à l'invention, la réticulation de la composition peut être réalisée au moyen de deux systèmes de réticulation. A titre d'exemple, on peut utiliser conjointement un système de réticulation basé sur le soufre et un système de réticulation basé sur les peroxydes organiques ou un système de réticulation basé sur une résine phénolique et un système de réticulation basé sur les peroxydes organiques. Selon la nature de I et III les compositions de l'invention peuvent être transformées par les techniques et matériels utilisés pour la mise en oeuvre des matières thermoplastiques : thermoformage, moulage par injection, extrusion, formage... Dans ce cas particulier les compositions de l'invention sont dites « à transformation thermoplastique ». A titre d'exemple de telles compositions on peut citer celles dans lesquelles l'élastomère I est constitué par un homopolymère, un copolymère ou un terpolymère dont la polymérisation a été réalisée au moyen d'un catalyseur métallocène et le polymère III est présent. Avantageusement III est une polyoléfine fonctionnalisée, de préférence une polyoléfine greffée. Elle peut être choisie parmi les polyoléfines greffées telles que citées plus haut. A titre d'exemple on peut les mélanges de I et III connus sous le nom de « végaprène ® ». Les compositions réticulées à transformation thermoplastique conformes à l'invention, tout en présentant des propriétés mécaniques en termes de dureté, de résistance à la rupture et d'allongement à la rupture équivalentes à celles des élastomères thermoplastiques de l'art antérieur précédemment évoqués, ont de meilleures propriétés de rémanence à la compression et à l'allongement que ces derniers. Cet avantage s'observe non seulement à court terme mais également à long terme où les compositions conformes à l'invention manifestent une tendance moindre au fluage. La présente invention a également pour objet un procédé de fabrication d'une composition réticulée telle que définie ci-dessus, caractérisé en ce qu'il comprend le mélange d'un élastomère et d'un copolymère séquence triblocs en présence éventuellement d'une polyoléfine greffée, d'un plastifiant, de charges et/ou d'adjuvants, et la réticulation de ce mélange par un système de réticulation convenablement choisi à une température appropriée. Selon un mode de mise en oeuvre préféré du procédé conforme à l'invention, la température à laquelle est effectuée la réticulation est comprise entre 150 et 320°C. Selon un mode de mise en oeuvre particulièrement préféré du procédé conforme à l'invention, celui-ci comprend : a) le mélange de l'élastomère, du copolymère séquence triblocs et du système de réticulation en présence, éventuellement, du polymère thermoplastique, de l'élastomère polyacrylique, du plastifiant, des charges et/ou des adjuvants ; b) le chauffage de ce mélange à une température comprise entre 150 et 320°C, et c) son maintien à cette température pendant un temps compris entre 1 et 15 minutes. Ce procédé peut être mis en oeuvre dans un mélangeur interne ou, en variante, dans une extrudeuse bi-vis ou un co-malaxeur du type BUSS. La masse résultante est, selon le cas, calandrée ou extrudée, puis refroidie et soumise à une granulation. Les granulés ainsi obtenus sont prêts à être transformés - par chauffage de ces granulés en feuilles, plaques, profilés, tubes ou autres produits désirés. La présente invention a aussi pour objet l'utilisation d'une composition réticulée telle que définie ci-avant pour la fabrication de joints et garnitures d'isolation et/ou d'étanchéité tels qu'employés pour l'isolation thermique, phonique et/ou l'étanchéité à l'eau et à l'humidité, notamment dans le bâtiment et par l'industrie automobile (garnitures de portières par exemple). La présente invention a, en outre, pour objet l'utilisation d'une telle composition dans la fabrication de conduits, de tubes, de tuyaux, de tubulures, de raccords ou analogues pour le transfert de fluides. A titre d'exemples, on peut citer les conduites, tuyaux et autres éléments prévus pour l'acheminement des fluides qui sont utilisés par l'industrie automobile dans les circuits de freinage, de refroidissement, d'assistance de direction ou encore de climatisation. On peut aussi citer l'utilisation de la composition réticulée de l'invention dans la fabrication de courroies, de pneus, de gaines de câbles électriques et de semelles de chaussures. La présente invention sera mieux comprise à l'aide du complément de description qui suit et qui se réfère à des exemples de réalisation de la composition réticulée conforme à l'invention. Parmi les compositions préférées de l'invention on peut citer à titre d'exemples non limitatifs les trois compositions suivantes :According to the invention, the crosslinking of the composition can be carried out by means of two crosslinking systems. For example, a crosslinking system based on sulfur and a crosslinking system based on organic peroxides or a crosslinking system based on a phenolic resin and a crosslinking system based on organic peroxides can be used together. Depending on the nature of I and III, the compositions of the invention can be transformed by the techniques and materials used for the implementation of thermoplastic materials: thermoforming, injection molding, extrusion, forming ... In this particular case, the compositions of the invention are said to be "thermoplastic transformation". By way of example of such compositions, mention may be made of those in which the elastomer I consists of a homopolymer, a copolymer or a terpolymer, the polymerization of which was carried out using a metallocene catalyst and the polymer III is present. Advantageously III is a functionalized polyolefin, preferably a grafted polyolefin. It can be chosen from grafted polyolefins as mentioned above. For example one can mixtures I and III known as "végaprène ®". The crosslinked thermoplastic transformation compositions in accordance with the invention, while having mechanical properties in terms of hardness, breaking strength and elongation at break equivalent to those of the previously mentioned thermoplastic elastomers of the prior art, have better remanence properties in compression and elongation than the latter. This advantage can be seen not only in the short term but also in the long term term in which the compositions in accordance with the invention show a less tendency to creep. The present invention also relates to a process for the manufacture of a crosslinked composition as defined above, characterized in that it comprises the mixing of an elastomer and a triblock block copolymer in the optional presence of a polyolefin grafted, of a plasticizer, fillers and / or adjuvants, and the crosslinking of this mixture by a crosslinking system suitably chosen at an appropriate temperature. According to a preferred embodiment of the process according to the invention, the temperature at which the crosslinking is carried out is between 150 and 320 ° C. According to a particularly preferred embodiment of the process in accordance with the invention, it comprises: a) mixing the elastomer, the triblock block copolymer and the crosslinking system in the presence, optionally, of the thermoplastic polymer, polyacrylic elastomer, plasticizer, fillers and / or adjuvants; b) heating this mixture to a temperature between 150 and 320 ° C, and c) keeping it at this temperature for a time between 1 and 15 minutes. This process can be implemented in an internal mixer or, as a variant, in a twin-screw extruder or a co-kneader of the BUSS type. The resulting mass is, as the case may be, calendered or extruded, then cooled and subjected to granulation. The granules thus obtained are ready to be processed - by heating these granules into sheets, plates, profiles, tubes or other desired products. The present invention also relates to the use of a crosslinked composition as defined above for the manufacture of joints and insulating and / or sealing gaskets as used for thermal, sound and / or waterproofing and humidity, especially in the building and by the automotive industry (door fittings for example). The present invention further relates to the use of such a composition in the manufacture of conduits, tubes, pipes, tubing, fittings or the like for the transfer of fluids. As examples, we can cite the pipes, hoses and other elements intended for conveying fluids which are used by the automobile industry in the braking, cooling, steering assistance or even air conditioning circuits. Mention may also be made of the use of the crosslinked composition of the invention in the manufacture of belts, tires, sheaths of electric cables and soles of shoes. The present invention will be better understood with the aid of the additional description which follows and which refers to exemplary embodiments of the crosslinked composition in accordance with the invention. Among the preferred compositions of the invention, the following three compositions may be mentioned as non-limiting examples:
1. compositions NR/BR pour applications dynamiques : butées, support moteur, 2. compositions EPDM, Végaprène 3 pour application statique : joint 3. compositions Végaprène 2 pour application du type enrobage câble, tuyau. Il va de soi, toutefois, que ces exemples sont donnés uniquement à titre d'illustrations de l'objet de l'invention dont ils ne constituent en aucune manière une limitation.1. NR / BR compositions for dynamic applications: stops, motor support, 2. EPDM, Vegaprene 3 compositions for static application: joint 3. Vegaprene 2 compositions for application of the cable, pipe coating type. It goes without saying, however, that these examples are given solely by way of illustrations of the subject of the invention of which they do not in any way constitute a limitation.
EXEMPLES : Différentes formulations ont été préparées selon le mode suivant : on introduit dans un mélangeur interne et sous un cisaillement approprié les ingrédients nécessaires à la réalisation de la composition réticulée. Tout en poursuivant le cisaillement, on porte la température interne des mélangeurs à une valeur de 170°C et, lorsque cette température est atteinte, on y maintient les mélanges pendant 5 minutes environ. On refroidit les masses ainsi obtenues à la sortie des mélangeurs et on les soumet à une granulation. On détermine : la dureté Shore A selon la méthode décrite dans la norme NF T 46-052, la résistance à la rupture (R/R) et l'allongement à la rupture (A/R) selon la méthode décrite dans la norme ISO 37, de chacune des compositions ainsi préparées, ainsi que : la déformation rémanente à la compression (DRC) au terme d'une compression de 25% appliquée pendant 22 heures à 100°C, selon la méthode décrite dans la norme ISO 815, et la déformation rémanente à l'allongement (DRA) au terme d'un allongement de 20% appliqué pendant 70 heures selon la méthode décrite dans la norme ISO 2285. Les tableaux suivants résument les compositions étudiées, exprimées en parts, ainsi que les résultats obtenus. A noter que les compositions référencées (a) ne contiennent pas de copolymères triblocs et constituent donc des exemples comparatifs. SBM désigne un tribloc II de masse molaire moyenne en nombre 60000 et contenant 50% en poids de PMMA. EXAMPLES: Different formulations were prepared according to the following method: the ingredients necessary for producing the crosslinked composition are introduced into an internal mixer and under appropriate shearing. While continuing the shearing, the internal temperature of the mixers is brought to a value of 170 ° C. and, when this temperature is reached, the mixtures are kept there for approximately 5 minutes. The masses thus obtained are cooled at the outlet of the mixers and subjected to granulation. The Shore A hardness is determined according to the method described in standard NF T 46-052, the breaking strength (R / R) and the elongation at break (A / R) according to the method described in ISO standard. 37, of each of the compositions thus prepared, as well as: the remanent compression deformation (DRC) at the end of a 25% compression applied for 22 hours at 100 ° C, according to the method described in standard ISO 815, and the remanent deformation at elongation (DRA) at the end an elongation of 20% applied for 70 hours according to the method described in standard ISO 2285. The following tables summarize the compositions studied, expressed in parts, as well as the results obtained. Note that the compositions referenced (a) do not contain triblock copolymers and therefore constitute comparative examples. SBM designates a triblock II of average molar mass in number 60,000 and containing 50% by weight of PMMA.
Tableau 2 '- Formulations à base de NR Table 2 '- NR-based formulations
A la lecture des tableaux 1 et 2 on constate qu'il y a amélioration importante du déchirement Delft qui est indicatif d'un meilleur comportement en fatigue (sous sollicitations mécaniques répétées) et ce sans que les autres caractéristiques importantes pour l'application soient modifiées (DRC, rebond). Ceci est une amélioration apportée aux formulations réticulées, qu 'elles aient ou non un mode de transformation thermoplastique. Tableau 3 : Compositions à base d'EPDM A reading of Tables 1 and 2 shows that there is a significant improvement in the Delft tear which is indicative of a better behavior in fatigue (under repeated mechanical stresses) without the other important characteristics for the application being modified. (DRC, rebound). This is an improvement to the crosslinked formulations, whether or not they have a thermoplastic transformation mode. Table 3: Compositions based on EPDM
Tableau 4 •' Formulations type Végaprène Table 4 • 'Vegaprene-type formulations
Les tableaux 3 et 4 montrent qu'il y a une amélioration de l'allongement et du déchirement Delft ce qui est important pour la mise en place et la résistance de la pièce. Tableau 5 : Formulation type Végaprène 2Tables 3 and 4 show that there is an improvement in the elongation and the Delft tear which is important for the positioning and the resistance of the part. Table 5: Typical formulation Vegaprene 2
On constate à la lecture de ce tableau que la DRC à haute température est améliorée. It can be seen from reading this table that the DRC at high temperature is improved.

Claims

REVENDICATIONS 1. Composition réticulée comprenant •' de 20 à 100 parties en poids d'au moins un élastomère (I) de 2 à 50 parties en poids d'au moins un copolymère séquence triblocs (II) dont au moins un bloc est constitué majoritairement de monomères méthacryliques, de 0 à 100 parties en poids d'au moins un polymère thermoplastique (III). CLAIMS 1. Crosslinked composition comprising • ' from 20 to 100 parts by weight of at least one elastomer (I) from 2 to 50 parts by weight of at least one triblock block copolymer (II) of which at least one block consists mainly methacrylic monomers, from 0 to 100 parts by weight of at least one thermoplastic polymer (III).
2. Composition selon la revendication 1 caractérisée en ce que le copolymère séquence triblocs (II) répond à la formule générale suivante Y-B-Y' dans laquelle : B est un bloc élastomère, thermodynamiquement incompatible avec les blocs Y et Y', Y et Y' ont ou n'ont pas la même composition chimique et au moins l'un d'eux est constitué majoritairement de monomères méthacryliques. 2. Composition according to claim 1 characterized in that the triblock block copolymer (II) corresponds to the following general formula YBY 'in which: B is an elastomer block, thermodynamically incompatible with blocks Y and Y', Y and Y 'have or do not have the same chemical composition and at least one of them consists mainly of methacrylic monomers.
3. Composition selon la revendication 2 caractérisée en ce que B est un bloc élastomère coréticulables avec l'élastomère (I) choisi parmi les polydiènes, les polydiènes partiellement ou totalement hydrogénés, les polyoléfines élastomères, les polyacrylates à chaîne longue, les élastomères nitriles, les copolymères acryliques de basse Tg comportant des fonctions vinyliques pendantes. 3. Composition according to claim 2 characterized in that B is an elastomer block which can be cross-linked with the elastomer (I) chosen from polydienes, partially or fully hydrogenated polydienes, elastomeric polyolefins, long chain polyacrylates, nitrile elastomers, low Tg acrylic copolymers containing pendant vinyl functions.
4. Composition selon la revendication 3 caractérisée en ce que B est un polydiène obtenu par la polymérisation d'au moins un monomère choisi dans le groupe comprenant le butadiène, l'isoprène, le 2,3-diméthyl-l,3-butadiène, le 1,3- pentadiène, le 2-phényl-l,3-butadiène. 4. Composition according to Claim 3, characterized in that B is a polydiene obtained by the polymerization of at least one monomer chosen from the group comprising butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-phenyl-1,3-butadiene.
5. Composition selon la revendication 2 caractérisée en ce que Y et Y' sont obtenus par la polymérisation d'au moins un monomère choisi parmi le styrène et ses dérivés, les méthacrylates d'alkyle à chaîne courte tels que le méthacrylate de méthyle, les monomères fonctionnels tels que l'acide acrylique, l'acide méthacrylique, le méthacrylate de glycidyle. 5. Composition according to claim 2 characterized in that Y and Y 'are obtained by the polymerization of at least one monomer chosen from styrene and its derivatives, short-chain alkyl methacrylates such as methyl methacrylate, functional monomers such as acrylic acid, methacrylic acid, glycidyl methacrylate.
6. Composition selon la revendication 5 caractérisée en ce que Y est un bloc constitué majoritairement de styrène et que Y' est un bloc contenant au moins 50% en poids de méthacrylate de méthyle. 6. Composition according to claim 5 characterized in that Y is a block mainly consisting of styrene and that Y 'is a block containing at least 50% by weight of methyl methacrylate.
7. Composition selon la revendication 6 dans laquelle le bloc Y' contient des fonctions imides. 7. Composition according to claim 6 in which the block Y 'contains imide functions.
8. Composition selon la revendication 1 caractérisée en ce que l'élastomère (I) est un composé choisi dans le groupe contenant les caoutchoucs naturels, les caoutchoucs synthétiques, les EPR, les EPDM, les élastomères à polymérisation métallocène tels que les poly(octène/éthylène), les polyacrylates à chaînes longues ou les polyoléfines élastomères modifiés ou non, les polyacrylates à chaîne longue tels que le polyacrylate de butyle ou le polyacrylate d'éthyle 2-héxyle et les élastomères fluorés (FPM) comme les copolymères à base de tetrafluoroéthylène et les silicones élastomères. 8. Composition according to claim 1 characterized in that the elastomer (I) is a compound chosen from the group containing natural rubbers, synthetic rubbers, EPRs, EPDMs, elastomers with metallocene polymerization such as poly (octene / ethylene), long chain polyacrylates or modified or unmodified elastomeric polyolefins, long chain polyacrylates such as polybutylacrylate or ethyl 2-hexylacrylate and fluorinated elastomers (FPM) such as copolymers based on tetrafluoroethylene and elastomeric silicones.
9. Composition selon la revendication 8 caractérisée en ce que l'élastomère (I) est le poly(octène / éthylène). 9. Composition according to claim 8 characterized in that the elastomer (I) is poly (octene / ethylene).
10. Composition selon la revendication 9 caractérisée en ce qu'elle peut être transformée comme un matériau thermoplastique. 10. Composition according to claim 9 characterized in that it can be transformed as a thermoplastic material.
11. Composition selon la revendication 1 caractérisée en ce que le polymère thermoplastique est choisi parmi les polyoléfines greffées telles que les polyéthylènes, les polypropylènes et les poly(éthylène/propylène) greffés d'acide acrylique, d'anhydride maléique ou de méthacrylate de glycidyle. 11. Composition according to claim 1 characterized in that the thermoplastic polymer is chosen from grafted polyolefins such as polyethylenes, polypropylenes and poly (ethylene / propylene) grafted with acrylic acid, maleic anhydride or glycidyl methacrylate .
12. Composition selon l'une quelconque des revendications précédentes caractérisée en ce qu'elle contient avant réticulation au moins un système de réticulation qui comprend un ou plusieurs agents de réticulation et un ou plusieurs promoteurs de réticulation. 12. Composition according to any one of the preceding claims, characterized in that it contains, before crosslinking, at least one crosslinking system which comprises one or more crosslinking agents and one or more crosslinking promoters.
13. Composition selon la revendication 12 caractérisée en ce que le système de réticulation comprend comme agent de réticulation un ou plusieurs peroxydes organiques choisis dans le groupe comprenant le peroxyde de dicumyle, le peroxde de l,3-bis-(t-butylisopropyl)benzène, le peroxyde de 2,5-diméthyl-2,5-bis-t-butyl- hexane et le 1,1 bis- (t-butyl)-3,3,5-triméthyl-cyclohexane, et comme promoteurs(s) de réticulation un ou plusieurs composés choisis dans le groupe comprenant l'oxyde de zinc, l'acide stéarique, le N,N-m-phénylène dimaléimide, les cyanures de triallyle ou de triisoallyle, les diméthacrylates, les triméthacrylates, les dicarylates et les triacrylates. 13. Composition according to claim 12 characterized in that the crosslinking system comprises as crosslinking agent one or more organic peroxides chosen from the group comprising dicumyl peroxide, l, 3-bis- (t-butylisopropyl) benzene peroxide , 2,5-dimethyl-2,5-bis-t-butylhexane peroxide and 1,1 bis- (t-butyl) -3,3,5-trimethyl-cyclohexane, and as promoters crosslinking one or more compounds chosen from the group comprising zinc oxide, stearic acid, N, Nm-phenylene dimaleimide, triallyl or triisoallyl cyanides, dimethacrylates, trimethacrylates, dicarylates and triacrylates.
14. Composition selon la revendication 12 caractérisée en ce que le système de réticulation est basé sur le soufre et comprend outre de l'oxyde de zinc et/ou de l'acide stéarique en tant que promoteurs de réticulation un ou plusieurs activateurs donneurs de soufre et éventuellement un agent anti-réversion. 14. Composition according to claim 12 characterized in that the crosslinking system is based on sulfur and comprises, in addition to zinc oxide and / or stearic acid as crosslinking promoters, one or more sulfur donor activators and possibly an anti-reversion agent.
15. Composition selon la revendication 12 caractérisée en ce que le système de réticulation comprend comme agent de réticulation une résine phénolique choisie parmi les résines méthyl phénolformaldéhyde et bromo-méthyl-phénolformaldéhyde alkylées réactives et comme promoteur de réticulation un polymère chloré éventuellement associé à de l'oxyde de zinc et/ou de l'acide stéarique. 15. A composition according to claim 12 characterized in that the crosslinking system comprises as crosslinking agent a phenolic resin chosen from methyl reactive alkyl phenolformaldehyde and bromo-methyl-phenolformaldehyde resins and as crosslinking promoter a chlorinated polymer optionally combined with l zinc oxide and / or stearic acid.
16. Composition selon l'une des revendications 13 à 15 caractérisée en ce que l'agent de réticulation et le promoteur de réticulation sont présents à une teneur comprise entre 0,5 et 12 parties en masse pour 100 parties du mélange. 16. Composition according to one of claims 13 to 15 characterized in that the crosslinking agent and the crosslinking promoter are present at a content of between 0.5 and 12 parts by mass per 100 parts of the mixture.
17. Composition réticulée selon l'une quelconque des revendications précédentes comprenant en outre un plastifiant et/ou des charges du type charges claires ou noirs de carbone et/ou des adjuvants. 17. Crosslinked composition according to any one of the preceding claims further comprising a plasticizer and / or fillers of the clear or black carbon fillers type and / or adjuvants.
18. Procédé de préparation d'une composition réticulée à transformation thermoplastique selon l'une des revendications précédentes caractérisé en ce qu'il comprend le mélange d'au moins un élastomère, d'au moins un copolymère séquence triblocs en présence éventuellement d'un polymère thermoplastique, d'un plastifiant, de charges et d'adjuvants et la réticulation de ce mélange par un système de réticulation approprié à une température convenablement choisie. 18. Process for the preparation of a crosslinked composition with thermoplastic transformation according to one of the preceding claims, characterized in that it comprises the mixture of at least one elastomer, of at least one triblock block copolymer, optionally in the presence of a thermoplastic polymer, plasticizer, fillers and adjuvants and the crosslinking of this mixture by an appropriate crosslinking system at a suitably chosen temperature.
19. Procédé selon la revendication 18 caractérisé en ce qu'il comprend la réticulation à une température comprise entre 150 et 320°C. 19. The method of claim 18 characterized in that it comprises crosslinking at a temperature between 150 and 320 ° C.
20. Procédé selon la revendication 18 ou 19 caractérisé en ce que la réticulation est opérée pendant un temps compris entre 1 et 15 minutes. 20. The method of claim 18 or 19 characterized in that the crosslinking is carried out for a time between 1 and 15 minutes.
21. Joints et garnitures d'isolation et/ou d'étanchéité comprenant une composition réticulée selon l'une quelconque des revendications 1 à 17. 21. Insulation and / or sealing joints and packings comprising a crosslinked composition according to any one of claims 1 to 17.
22. Utilisation des joints et garnitures d'isolation et/ou d'étanchéité selon la revendication 21 dans le bâtiment.22. Use of joints and insulating and / or sealing gaskets according to claim 21 in the building.
23. Utilisation des joints et garnitures d'isolation et/ou d'étanchéité selon la revendication 21 dans l'industrie automobile. 23. Use of seals and insulating and / or sealing gaskets according to claim 21 in the automotive industry.
24. Conduits tels que tubes, tuyaux, tubulures, raccords comprenant une composition réticulée selon l'une quelconque des revendications 1 à 17. 24. Ducts such as tubes, pipes, tubes, fittings comprising a crosslinked composition according to any one of claims 1 to 17.
25. Utilisation des compositions selon l'une des revendications 1 à 17 dans la fabrication de câbles électriques. 25. Use of the compositions according to one of claims 1 to 17 in the manufacture of electric cables.
26. Utilisation des compositions selon l'une des revendications 1 à 17 dans la fabrication de pneus. 26. Use of the compositions according to one of claims 1 to 17 in the manufacture of tires.
27. Utilisation des compositions selon l'une des revendications 1 à 17 pour la fabrication de courroies. 27. Use of the compositions according to one of claims 1 to 17 for the manufacture of belts.
28. Utilisation des compositions selon l'une des revendications 1 à 17 pour la fabrication de semelles de chaussures. 28. Use of the compositions according to one of claims 1 to 17 for the manufacture of shoe soles.
EP05731113A 2004-02-24 2005-02-23 Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same Withdrawn EP1718698A1 (en)

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FR0401826A FR2866651A1 (en) 2004-02-24 2004-02-24 Cross linking composition, useful in e.g. joints and insulation accessories that are useful in automobile industries, comprises an elastomer, a triblock copolymer sequence and a polyolefin graft
FR0408713 2004-08-06
PCT/FR2005/000420 WO2005082996A1 (en) 2004-02-24 2005-02-23 Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same

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