Vibration-damping device containing a rubber compound

Description

[0001] The present invention relates to rubber vibration isolation articles.

[0002] Rubber anti-vibration devices, also known as rubber vibration dampers, are commonly used, particularly in the automotive industry, but also in any component that experiences or generates vibrations. These devices specifically reduce vibrations originating from a machine's vibration source, such as an engine, to prevent damage to other machine components or to improve user comfort.

[0003] It is known to use ethylene-propylene-diene monomer (EPDM) copolymers as the main component of anti-vibration articles, due to their ability to reduce vibrations at temperatures exceeding 60°C. Application KR10-2014-0078243, for example, describes compositions for anti-vibration articles comprising EPDM, carbon black, a plasticizing oil, and a crosslinking system.

[0004] Anti-vibration rubber products must possess numerous properties. In particular, they must exhibit good ozone resistance to limit the appearance of cracks and delay or even prevent tearing of these products.

[0005] Furthermore, these items should advantageously exhibit low energy dissipation during normal machine operation, i.e., at low frequencies (around 1 Hz), in order to minimize heat generation and thus increase the lifespan of the anti-vibration devices. Conversely, they should advantageously exhibit high energy dissipation at high frequencies (between 20 and 700 Hz), which correspond to vibration peaks that can reach the resonant frequency of the anti-vibration device. This is necessary to minimize vibrations transmitted to the rest of the machine and potentially to the machine operator, and potentially also to reduce the noise perceived by the operator.

[0006] Thus, manufacturers are always looking for solutions to increase the lifespan of anti-vibration products, for example by improving ozone resistance and / or reducing low-frequency energy dissipation, while further reducing high-frequency vibrations.

[0007] Continuing her research, the Applicant unexpectedly discovered that the use of a particular highly saturated copolymer makes it possible to solve this technical problem.

[0008] Thus, the invention relates to an anti-vibration rubber article comprising a rubber composition based on at least: an elastomeric matrix comprising at least one copolymer containing ethylene units and 1,3-diene units, the mole fraction of ethylene units in the copolymer being in the range of more than 50% to 95%, a reinforcing filler comprising at least one carbon black having a specific surface area BET of between 5 and 110 m² / g, a crosslinking system comprising at least one peroxide and a crosslinking co-agent selected from the group consisting of (meth)acrylate compounds, maleimide compounds, allylic compounds, vinyl compounds and mixtures thereof, said article being chosen from the group consisting of rubber supports, rubber mounts, rubber bushings, rubber bushings, rubber bearings, rubber shock absorber pulleys, rubber hoses, rubber pads and rubber anti-vibration panels. I- DEFINITIONS

[0009] The term "based on" used to define the components of a catalytic system or composition refers to the mixture of these components, or the product of the reaction of some or all of these components with each other, at least partially, during the various stages of manufacturing the catalytic system or composition. In the case of a composition, it may thus be in a fully or partially crosslinked state, or in a non-crosslinked state.

[0010] By "elastomer matrix" we mean all the elastomers in the composition, including the copolymer defined below.

[0011] Unless otherwise stated, the rates of units resulting from the insertion of a monomer into a copolymer are expressed as a mole percentage relative to the total monomer units of the copolymer.

[0012] The expression "part by weight per hundred parts by weight of elastomer" (or pce) is to be understood in the context of the present invention as the part, by mass per hundred parts of elastomer present in the rubber composition under consideration.

[0013] In this document, unless expressly stated otherwise, all percentages (%) shown are percentages (%) by mass.

[0014] On the other hand, any interval of values ​​designated by the expression "between a and b" represents the domain of values ​​from greater than a to less than b (that is, excluding the bounds a and b), while any interval of values ​​designated by the expression "from a to b" means the domain of values ​​from a to b (that is, including the strict bounds a and b). In this context, when an interval of values ​​is designated by the expression "from a to b," it also and preferentially designates the interval represented by the expression "between a and b."

[0015] The compounds mentioned in the description can be of fossil origin or bio-based. In the latter case, they may be partially or entirely derived from biomass or obtained from renewable raw materials derived from biomass. Similarly, the compounds mentioned may also come from the recycling of previously used materials; that is, they may be partially or entirely produced through a recycling process, or obtained from raw materials themselves derived from a recycling process. This includes, in particular, polymers, plasticizers, fillers, etc.

[0016] Unless otherwise stated, all glass transition temperature "Tg" values ​​described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to ASTM D3418 (1999). II- DESCRIPTION OF THE INVENTION II-1 Elastomer Matrix

[0017] According to the invention, the elastomeric matrix of the composition comprises at least one copolymer containing ethylene units and 1,3-diene units, the mole fraction of ethylene units in the copolymer being in a range from more than 50% to 95%.

[0018] In this document, the "copolymer containing ethylene units and 1,3-diene units, the mole fraction of ethylene units in the copolymer being in the range of more than 50% to 95%" may be referred to as "the copolymer" or as "the copolymer containing ethylene units and 1,3-diene units" for the sake of simplifying the wording.

[0019] The term "copolymer containing ethylene and 1,3-diene units" means any copolymer comprising, within its structure, at least ethylene and 1,3-diene units. The copolymer may thus comprise monomer units other than ethylene and 1,3-diene units. For example, the copolymer may also comprise alpha-olefin units, in particular alpha-olefin units having from 3 to 18 carbon atoms, advantageously having from 3 to 6 carbon atoms. For example, the alpha-olefin units may be selected from the group consisting of propylene, butene, pentene, hexene, or mixtures thereof.

[0020] The well-known expression "ethylene unit" refers to the -(CH2-CH2)- motif resulting from the insertion of ethylene into the elastomer chain.

[0021] The term "1,3-diene unit" is commonly used to refer to units resulting from the insertion of 1,3-diene by a 1,4-addition, a 1,2-addition, or a 3,4-addition in the case of isoprene. 1,3-diene units are those of, for example, a 1,3-diene or a mixture of 1,3-dienes, the 1,3-diene(s) having from 4 to 12 carbon atoms, such as, in particular, 1,3-butadiene and isoprene. Preferably, 1,3-diene units are 1,3-butadiene units.

[0022] Advantageously, the ethylene units in the copolymer represent between 55% and 90% by mole of the monomer units of the copolymer.

[0023] Advantageously, the copolymer containing ethylene units and 1,3-diene units is an ethylene-1,3-diene copolymer, preferably an ethylene-1,3-butadiene copolymer, that is, the copolymer does not contain units other than ethylene and 1,3-diene, preferably no units other than ethylene and 1,3-butadiene.

[0024] When the copolymer is a copolymer of ethylene and a 1,3-diene, it advantageously contains units of formula (I) and / or (II). The presence of a saturated 6-member cyclic motif, 1,2-cyclohexanediyl, of formula (I) as a monomer unit in the copolymer can result from a series of very specific insertions of ethylene and 1,3-butadiene into the polymer chain during its growth. -CH 2 -CH(CH=CH 2 )- (II)

[0025] For example, the copolymer of ethylene and a 1,3-diene may be devoid of formula units (I). In this case, it preferably contains formula units (II).

[0026] When the copolymer of ethylene and a 1,3-diene comprises units of formula (I) or units of formula (II) or units of formula (I) and units of formula (II), the molar percentages of units of formula (I) and units of formula (II) in the copolymer, respectively o and p, preferably satisfy the following equation (eq. 1), more preferably equation (eq. 2), o and p being calculated on the basis of all the monomer units of the copolymer. 0 < o + p ≤ 25 0 < o + p < 20

[0027] According to the invention, the copolymer, preferably the copolymer of ethylene and a 1,3-diene (preferably of 1,3-butadiene), is a statistical copolymer.

[0028] Advantageously, the number-average mass (Mn) of the copolymer, preferably of the copolymer of ethylene and a 1,3-diene (preferably of 1,3-butadiene) is in the range of 100,000 to 300,000 g / mol, preferably of 150,000 to 250,000 g / mol.

[0029] The Mn of the copolymer is determined in a known manner, by size exclusion chromatography (SEC) as described in the examples.

[0030] The copolymer can be obtained by various synthetic methods known to those skilled in the art, depending in particular on the desired microstructure of the copolymer. Generally, it can be prepared by copolymerization of at least one 1,3-diene, preferably 1,3-butadiene, and ethylene, using known synthetic methods, particularly in the presence of a catalytic system comprising a metallocene complex. Examples include catalytic systems based on metallocene complexes, which are described in documents EP 1 092 731, WO 2004035639, WO 2007054223, and WO 2007054224 on behalf of the Applicant. The copolymer, including when it is statistical, can also be prepared by a process using a preformed type catalytic system such as those described in documents WO 2017093654 A1, WO 2018020122 A1 and WO 2018020123 A1.

[0031] The copolymer can be made up of a mixture of copolymers containing ethylene units and diene units that differ from each other by their microstructures and / or by their macrostructures.

[0032] Advantageously, the proportion of the copolymer containing ethylene and 1,3-diene units in the composition is in the range of 30 to 100 parts per cent, 50 to 100 parts per cent, and preferably 80 to 100 parts per cent. The elastomeric matrix may advantageously comprise, as the elastomer, only the copolymer containing ethylene and 1,3-diene units. Compositions according to the invention comprising more than 50 parts per cent, and preferably more than 80 parts per cent, of the copolymer containing ethylene and 1,3-diene units are particularly advantageous for use in anti-vibration articles intended to withstand temperatures above 85°C.

[0033] Alternatively, the elastomer matrix may further comprise a diene elastomer distinct from the copolymer containing ethylene units and 1,3-diene units (also referred to herein as "the other elastomer").

[0034] When the composition includes another elastomer, the percentage of the copolymer containing ethylene units and 1,3-diene units in the composition may be in the range of 30 to 90 parts per cent, preferably 50 to 80 parts per cent, the percentage of the other elastomer being in the range of 10 to 70 parts per cent, preferably 20 to 50 parts per cent.

[0035] The other elastomer in the elastomer matrix of the tire according to the invention is preferably chosen from the group of highly unsaturated diene elastomers such as polybutadienes (abbreviated "BR"), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers, and mixtures of these elastomers. A "highly unsaturated diene elastomer" is generally understood to be a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of diene-derived motifs or units (conjugated dienes) greater than 50% (mole percent).

[0036] Preferably, the other elastomer is chosen from the group consisting of polyisoprenes having a molar cis-1,4 bond ratio greater than 90%. It may be synthetic polyisoprene, natural rubber, or a mixture thereof. Preferably, the other elastomer is a natural rubber. II-2 Reinforcing Load

[0037] According to the invention, the composition comprises a reinforcing filler comprising at least one carbon black whose specific surface area BET is between 5 and 110 m² / g.

[0038] The blacks usable within the scope of the present invention can be any black conventionally used in pneumatic or non-pneumatic tires or their treads (so-called pneumatic-grade blacks). Among these, particularly noteworthy examples include reinforcing carbon blacks of the 300, 400, 500, 600, or 700 series (ASTM grades), such as N326, N330, N339, N347, N375, N550, N683, and N772. These carbon blacks can be used in isolation, as commercially available, or in any other form, for example, as a carrier for certain rubber additives used. The carbon blacks could, for example, already be incorporated into the diene elastomer, particularly isoprene, in the form of a masterbatch (see, for example, applications WO 97 / 36724 or WO 99 / 16600). Mixtures of several carbon blacks can also be used in the prescribed rates.

[0039] Advantageously, said carbon black has a specific BET surface area of ​​between 10 and 100 m² / g, preferably between 20 and 80 m² / g, and even more preferably between 20 and 70 m² / g. The specific BET surface area of ​​carbon blacks is measured according to ASTM D6556-10 [multipoint method (minimum 5 points) - gas: nitrogen - relative pressure range P / P0: 0.1 to 0.3].

[0040] Carbon black, preferably said carbon black, can represent more than 50%, preferably more than 80%, or even 100%, by weight of the reinforcing charge.

[0041] The reinforcing filler may also include silica as a reinforcing filler, i.e. silica used in combination with a coupling agent well known to those skilled in the art.

[0042] The silica may be any silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface area and a CTAB specific surface area both less than 450 m² / g, preferably from 30 to 400 m² / g, in particular from 60 to 300 m² / g. The silica advantageously has a BET specific surface area in the range of 125 to 200 m² / g and / or a CTAB specific surface area in the range of 140 to 170 m² / g.

[0043] The specific surface area BET of silica is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" (Vol. 60, page 309, February 1938), and more specifically according to a method adapted from the standard NF ISO 5794-1, Annex E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - degassing under vacuum: one hour at 160°C - relative pressure range w / in: 0.05 to 0.17].

[0044] The CTAB specific surface area values ​​of silica were determined according to standard NF ISO 5794-1, Annex G of June 2010. The process is based on the adsorption of CTAB (N-hexadecyl-N,N,N-trimethylammonium bromide) on the "external" surface of the charge.

[0045] Any type of precipitated silica can be used, including highly dispersible precipitated silicas (known as "HDS" for "highly dispersible" or "highly dispersible silica"). These precipitated silicas, whether highly dispersible or not, are well known to those skilled in the art. Examples include the silicas described in applications WO03 / 016215-A1 and WO03 / 016387-A1. Among the commercial HDS silicas, one can notably use the silicas “Ulsil ®< 5000GR”, “Ulsil ®< 7000GR” from the company Evonik, the silicas “Zeosil ®< 1085GR”, “Zeosil ®< 1115 MP”, “Zeosil ®< 1165MP”, “Zeosil ®< Premium 200MP”, “Zeosil ®< HRS 1200 MP” from the Solvay Company.As non-HDS silica, the following commercial silicas may be used: “Ultrasil ®< VN2GR”, “Ultrasil ®< VN3GR” silicas from Evonik, “Zeosil ®< 175GR” silica from Solvay, “Hi-Sil EZ120G(-D)”, “Hi-Sil EZ160G(-D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210”, “Hi-Sil HDP 320G” silicas from PPG.

[0046] When silica is used, it advantageously represents 5% to 50%, preferably 10% to 40% by weight of the reinforcing charge.

[0047] To couple silica to the diene elastomer, a well-known coupling agent (or bonding agent) can be used to ensure sufficient chemical and / or physical connection between the inorganic filler (the surface of its particles) and the diene elastomer. Organosilanes or polyorganosiloxanes, at least bifunctional, are particularly used. "Bifunctional" means a compound possessing a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound might include a first functional group comprising a silicon atom, which is capable of interacting with the hydroxyl groups of an inorganic filler, and a second functional group comprising a sulfur atom, which is capable of interacting with the diene elastomer.

[0048] Preferably, organosilanes are chosen from the group consisting of polysulfide organosilanes (symmetric or asymmetric) such as bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT and marketed under the name "Si69" by Evonik, or bis-(triethoxysilylpropyl) disulfide, abbreviated TESPD and marketed under the name "Si75" by Evonik; polyorganosiloxanes; mercaptosilanes; and blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl) octanethioate, marketed by Momentive under the name "NXT Silane". More preferably, the organosilane is a polysulfide organosilane.

[0049] When silica is used, the coupling agent content in the composition according to the invention can easily be adjusted by a person skilled in the art. Typically, the coupling agent content ranges from 0.5% to 15% by weight relative to the amount of silica.

[0050] Preferably, the percentage of said carbon black, preferably the percentage of reinforcing filler, in the composition according to the invention is between 20 and 70 parts per cent, preferably in the range of 30 to 60 parts per cent. When said carbon black is the only reinforcing filler, its percentage in the composition is preferably between 20 and 70 parts per cent, preferably in the range of 30 to 60 parts per cent.

[0051] When silica is present in the composition, the carbon black content may be in the range of 19 to 69 parts per annum, preferably 27 to 57 parts per annum, and the silica content in the range of 1 to 35 parts per annum, preferably 3 to 24 parts per annum. II-3 Crosslinking System

[0052] According to the invention, the crosslinking system of the composition comprises at least one peroxide and a crosslinking co-agent selected from the group consisting of (meth)acrylate compounds, maleimide compounds, allylic compounds, vinyl compounds and mixtures thereof. Peroxide

[0053] Advantageously, peroxide is an organic peroxide.

[0054] Organic peroxide refers to an organic compound, meaning one containing carbon and an -OO- group (two oxygen atoms linked by a single covalent bond). During the crosslinking process, the organic peroxide decomposes at its unstable OO- bond into free radicals. These free radicals enable the formation of crosslinks.

[0055] The organic peroxide is preferably chosen from the group comprising or consisting of dialkyl peroxides, monoperoxycarbonates, diacyl peroxides, peroxyketals or peroxyesters.

[0056] Preferably, the dialkyl peroxides are selected from the group comprising or consisting of dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-amylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3, α,α'-di-[(t-butylperoxy)isopropyl]benzene, α,α'-di-[(t-amylperoxy)isopropyl]benzene, di-t-amyl peroxide, 1,3,5-tri-[(t-butylperoxy)isopropyl]benzene, 1,3-dimethyl-3-(t-butylperoxy)butanol, and 1,3-dimethyl-3-(t-amylperoxy)butanol.

[0057] Some monoperoxycarbonates such as OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate, OO-tert-butyl-O-isopropyl monoperoxycarbonate and OO-tert-amyl-O-2-ethyl hexyl monoperoxycarbonate, can also be used.

[0058] Among the diacyl peroxides, the preferred peroxide is benzoyl peroxide.

[0059] Among the peroxyketals, preferred peroxides are chosen from the group comprising or consisting of 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl 4,4-di-(t-butylperoxy)valerate, ethyl 3,3-di-(t-butylperoxy)butyrate, 2,2-di-(t-amylperoxy)propane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or cyclic trimer of methyl ethyl ketone peroxide), 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, n-butyl 4,4-bis(t-amylperoxy)valerate, ethyl 3,3-di(t-amylperoxy)butyrate, the 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane and mixtures thereof. Preferably, the peroxyesters are selected from the group consisting of tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate and tert-butylperoxy-3,5,5-trimethylhexanoate.

[0060] In summary, the organic peroxide is, particularly preferred, chosen from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, ditertbutyl peroxide, tertbutylcumyl peroxide, 2,5-bis(tertbutylperoxy)-2,5-dimethylhexane, n-butyl-4,4'-di(tert-butylperoxy) valerate, OO-(t-butyl)-O-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,3(4)-bis(tert-butylperoxyisopropyl)benzene and mixtures thereof.Preferably, the organic peroxide is chosen from the group consisting of dicumyl peroxide, n-butyl-4,4'-di(tert-butylperoxy)-valerate, OO-(t-butyl) O-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,3(4)-bis(tert-butylperoxyisopropyl)benzene and mixtures thereof.

[0061] Examples of commercially available peroxides usable within the framework of the present invention include "Dicup" from Hercules Powder Co., "Perkadox Y12" from Noury ​​van der Lande, "Peroximon F40" from Montecatini Edison SpA, "Trigonox" from Noury ​​van der Lande, "Varox" from RTVanderbilt Co., and "Luperko" from Wallace & Tiernan, Inc.

[0062] The peroxide content in the composition is advantageously within a range of 0.5 to 10 parts per liter, preferably from 1 to 5 parts per liter. Crosslinking co-agent

[0063] According to the invention, the crosslinking co-agent is chosen from the group consisting of (meth)acrylate compounds, maleimide compounds, allylic compounds, vinyl compounds and mixtures thereof.

[0064] Preferably, the co-agent comprises a (meth)acrylate compound, in the form of a metal salt, or ester, or in polymeric form.

[0065] Preferably, the crosslinking co-agent comprises an acrylate derivative of formula (III): [X] p A (III) in which, [X]p corresponds to a radical of formula (IV): in which, ° ∘ R 1 , R 2 and R 3 independently represent a hydrogen atom or a C 1 -C 8 hydrocarbon group chosen from the group consisting of linear, branched or cyclic alkyl groups, alkylaryl groups, aryl groups and aralkyls, and possibly interrupted by one or more heteroatoms, R 2 and R 3 being able to form together a non-aromatic ring, ° ∘ (*) represents the point of attachment of the radical of formula (IV) to A, A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom, or a C 1 -C 30 hydrocarbon group possibly interrupted and / or substituted by one or more heteroatoms, A comprising p free valences, p having a value from 2 to 6, it being understood that the 2 to 6 radicals X are identical or different.

[0066] According to the invention, the bond between X and A can be an ionic bond or a covalent bond. Those skilled in the art understand that when A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, particularly Zn or Mg, the bond between X and A is an ionic bond. Furthermore, when A represents a carbon atom or a C1-C30 hydrocarbon group, those skilled in the art understand that the bond between X and A is a covalent bond.

[0067] A cyclic alkyl group is understood to be an alkyl group comprising one or more rings.

[0068] By hydrocarbon group or chain interrupted by one or more heteroatoms, we mean a group or chain comprising one or more heteroatoms, each heteroatom being contained between two carbon atoms of said group or chain, or between a carbon atom of said group or chain and another heteroatom of said group or chain, or between two other heteroatoms of said group or chain.

[0069] By hydrocarbon group or chain substituted by one or more heteroatoms, we mean a group or chain comprising one or more heteroatoms, each heteroatom being linked to the hydrocarbon group or chain by a covalent bond without interrupting the hydrocarbon group or chain.

[0070] The heteroatom(s) of A may be chosen from the group consisting of oxygen, sulfur, nitrogen, silicon, phosphorus atoms, and their combinations. Preferably, the heteroatom(s) of A are chosen from the group consisting of oxygen and sulfur atoms. Even more preferably, the heteroatom(s) of A are oxygen atoms.

[0071] In other words, A advantageously represents a C4-C30 hydrocarbon group, linear, branched, or cyclic, interrupted and / or substituted by one or more heteroatoms selected from oxygen, sulfur, nitrogen, silicon, phosphorus atoms and their combinations, preferably selected from the group consisting of oxygen and sulfur atoms. Preferably, A further advantageously represents a C4-C30 hydrocarbon group, linear, branched, or cyclic, preferably linear or branched, interrupted and / or substituted by one or more oxygen and / or sulfur atoms, preferably interrupted and / or substituted by one or more oxygen atoms.

[0072] Preferably, A represents a C4-C30 hydrocarbon group, linear, branched or cyclic, preferably linear or branched, interrupted by one or more oxygen and / or sulfur atoms, preferably interrupted by one or more oxygen atoms. Even more preferably, A represents a C4-C30 hydrocarbon group, linear or branched, interrupted by one or more oxygen atoms.

[0073] When A represents a hydrocarbon group in C4-C30, it may be, for example, a hydrocarbon group in C5-C20, preferably in C6-C16.

[0074] When A includes a cyclic hydrocarbon group, it may be a non-aromatic or aromatic cyclic hydrocarbon group.

[0075] The heteroatom(s) of the radicals R1, R2, R3 and A can be, independently of each other, atoms of oxygen, sulfur, nitrogen, phosphorus or silicon, preferably atoms of oxygen or nitrogen.

[0076] Regardless of the nature of the radical A, R1, R2 and R3 can independently represent a hydrogen atom, a methyl group or an ethyl group, preferably R1, R2 and R3 independently represent a hydrogen atom or a methyl group.

[0077] Advantageously, R1 can represent a methyl group and R2 and R3 can each represent a hydrogen atom. Alternatively, R1, R2, and R3 can each represent a hydrogen atom.

[0078] The valence number p depends on the nature of the radical A. According to the invention, p can be 2, 3, 4, 5 or 6. Preferably, p is 2, 3 or 4, preferably 2 or 3, preferably 2.

[0079] Advantageously, in which in the acrylate derivative of formula (III), regardless of the groups R1, R2 and R3: A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a hydrocarbon group in C1-C13, preferably in C1-C8, A comprising p free valences, p having a value from 2 to 4, it being understood that the 2 to 4 radicals X are identical or different, preferably identical.

[0080] According to the invention, when A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, it may be, for example, an atom chosen from the group consisting of Zn, Mg and Fe, preferably from the group consisting of Zn and Mg.

[0081] When A represents a hydrocarbon group in C1-C13, preferably C1-C8, it may be, for example, a hydrocarbon group in C1-C7, preferably in C1-C6.

[0082] A can represent a C1-C13 hydrocarbon group chosen from the group consisting of the following radicals: in which, m is an integer from 1 to 13, and (*) represents the point of attachment of A to the radical of formula (IV).

[0083] Advantageously, the hydrocarbon group in C1-C13 is a radical *-(CH2)m-* in which m is an integer from 1 to 13, preferably from 1 to 8, preferably from 1 to 6, and (*) represents the point of attachment of A to the radical of formula (III).

[0084] Thus, according to the invention, the acrylate derivative of formula (III) can be selected from zinc dimethacrylate (ZDMA), magnesium dimethacrylate (MgDMA), zinc diacrylate (ZDA), magnesium diacrylate (MgDA), trimethylopropane trimethylacrylate (TMPTMA), trimethylolproprane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDDA), and mixtures thereof. Preferably, the acrylate derivative of formula (III) can be selected from zinc dimethacrylate (ZDMA), zinc diacrylate (ZDA), trimethylopropane trimethylacrylate (TMPTMA), and mixtures thereof.

[0085] For example, commercially available diacrylate derivatives include zinc diacrylate (ZDA) "DYMALINK 633" from Cray Valley, zinc dimethacrylate (ZDMA) "DYMALINK 634" from Cray Valley, trimethylolpropane trimethacrylate (TMPTMA) "SR351" from Sartomer, and 1,6-hexanediol diacrylate (HDDA) from Sigma-Aldrich.

[0086] Advantageously, the rate of crosslinking co-agent in the composition according to the invention is in a range of 1 to 20 parts per annum, preferably from 2 to 10 parts per annum, preferably between 2 and 5 parts per annum.

[0087] Advantageously, the amount of peroxide in the composition is in the range of 10% to 100% by weight, preferably between 20% and 80% by weight, relative to the weight of crosslinking co-agent in the composition.

[0088] Advantageously also, the ratio of the reinforcing charge rate to the crosslinking co-agent rate is in the range of 3 to 40, preferably 6 to 30. Sulfur

[0089] Furthermore, the composition according to the invention is advantageously free of sulfur as a vulcanizing agent, or contains less than 0.5 parts per annum, preferably less than 0.3 parts per annum, preferably less than 0.2 parts per annum, and preferably less than 0.1 parts per annum. The sulfur may be molecular sulfur or derived from a sulfur-donating agent, such as alkylphenol disulfides (APDS). II-4 Possible Additives

[0090] Rubber compositions intended for use in anti-vibration articles may optionally also include all or some of the usual additives normally used in elastomer compositions for such articles, such as plasticizers (such as plasticizing oils and / or plasticizing resins), pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents, reinforcing resins (such as described for example in application WO 02 / 10269) or blowing agents. II-5 Preparation of rubber compositions

[0091] The compositions according to the invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: A first thermomechanical working or mixing phase (the so-called "non-productive" phase) can be carried out in a single thermomechanical step during which all the necessary constituents, including the elastomeric matrix, the reinforcing filler, and any other miscellaneous additives, with the exception of the crosslinking system, are introduced into a suitable mixer such as a standard internal mixer (for example, a Banbury-type mixer). The incorporation of any filler into the elastomer can be carried out in one or more stages by thermomechanical mixing.Where the filler is already fully or partially incorporated into the elastomer as a masterbatch, as described, for example, in applications WO 97 / 36724 or WO 99 / 16600, the masterbatch is mixed directly. If necessary, other elastomers or fillers present in the composition that are not in masterbatch form are then incorporated, along with any other miscellaneous additives other than the crosslinking system. The non-productive phase can be carried out at high temperature, up to a maximum temperature between 110°C and 200°C, preferably between 130°C and 185°C, for a duration generally between 2 and 10 minutes.a second mechanical working phase (the so-called "productive" phase), which can be carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature, typically below 120°C, for example between 40°C and 100°C. The crosslinking system is then incorporated, and the whole is then mixed for a few minutes, for example between 5 and 15 min.

[0092] Such phases have been described for example in applications EP-A-0501227, EP-A-0735088, EP-A-0810258, WO00 / 05300 or WO00 / 05301.

[0093] The resulting final composition is then calendered, for example, into a sheet or plate, particularly for laboratory characterization, or extruded (or co-extruded with another rubber compound) into a semi-finished product (or profile) of rubber usable, for example, as anti-vibration panels, anti-vibration strips, or isolation pads. Alternatively, the final composition can be molded and cross-linked using techniques known to those skilled in the art to produce mounts and bushings. These products can then be used to manufacture anti-vibration devices, using techniques known to those skilled in the art.

[0094] The composition can be either in the raw state (before crosslinking or vulcanization), or in the cooked state (after crosslinking or vulcanization), can be a semi-finished product which can be used as an anti-vibration article, or in an anti-vibration article, for example associated with a metal part, the whole constituting the anti-vibration article.

[0095] The crosslinking of the composition can be carried out in a manner known to those skilled in the art, for example at a temperature between 100°C and 200°C, under pressure. II-6 Anti-vibration articles

[0096] Rubber compositions according to the invention find numerous applications in anti-vibration articles or devices, particularly as vibration isolators or dampers.

[0097] The present invention relates to an anti-vibration article comprising at least one rubber element according to the invention, said article being chosen from the group consisting of rubber supports, rubber mounts, rubber bushings, rubber pads, rubber bearings, rubber shock absorber pulleys, rubber hoses, rubber buffers and rubber anti-vibration panels.

[0098] Rubber supports can be used, for example, as seismic mounts or bridge bearings. Rubber supports can be of any shape, such as cylindrical or conical supports. Rubber bushings can be ribbed, sandwich, or multi-layer ribbed bushings. Rubber bearings can be central bearings or slide bearings.

[0099] Preferably, the anti-vibration article comprising at least one rubber element is chosen from the group consisting of rubber mounts and anti-vibration panels. Preferably, it is an anti-vibration panel. IV- EXAMPLES IV-1 Measurements and tests used Determination of the microstructure of elastomers:

[0100] The microstructure of ethylene-butadiene copolymers is determined by ¹H NMR analysis, supplemented by ¹³C NMR analysis when the resolution of the ¹H NMR spectra is insufficient for the identification and quantification of all species. Measurements are performed using a BRUKER 500 MHz NMR spectrometer at frequencies of 500.43 MHz for proton observation and 125.83 MHz for carbon observation. For insoluble elastomers that swell in a solvent, a 4 mm z-grad HRMAS probe is used, enabling proton and carbon observation in proton-decoupled mode. Spectra are acquired at rotation speeds of 4000 Hz to 5000 Hz. For measurements on soluble elastomers, a liquid NMR probe is used, enabling proton and carbon observation in proton-decoupled mode.Insoluble samples are prepared in rotors filled with the material being analyzed and a deuterated solvent that induces swelling, typically deuterated chloroform (CDCl3). The solvent used must always be deuterated, and its chemical composition can be adjusted by those skilled in the art. The quantities of material used are adjusted to obtain spectra with sufficient sensitivity and resolution. Soluble samples are dissolved in a deuterated solvent (approximately 25 mg of elastomer in 1 mL), typically deuterated chloroform (CDCl3). The solvent or solvent blend used must always be deuterated, and its chemical composition can be adjusted by those skilled in the art. This applies to both soluble and swollen samples. For proton NMR, a single-pulse 30° sequence is used. The spectral window is set to observe all the resonance lines belonging to the molecules being analyzed.The number of accumulations is adjusted to obtain a signal-to-noise ratio sufficient for quantifying each motif. The recycle time between each pulse is adapted to obtain a quantitative measurement. For carbon NMR, a simple 30° pulse sequence is used with proton decoupling only during acquisition to avoid Nuclear Overhauser Effects (NOE) and maintain quantitative accuracy. The spectral window is adjusted to observe all resonance lines belonging to the analyzed molecules. The number of accumulations is adjusted to obtain a signal-to-noise ratio sufficient for quantifying each motif. The recycle time between each pulse is adapted to obtain a quantitative measurement. NMR measurements are performed at 25°C. Determination of the macrostructure of polymers by size exclusion chromatography (SEC): a) Principle of measurement:

[0101] Size exclusion chromatography (SEC) separates macromolecules in solution according to their size using columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, with the largest being eluted first.

[0102] Combined with three detectors (3D), a refractometer, a viscometer, and a 90° light scattering detector, SEC allows for the determination of the absolute molar mass distribution of a polymer. The various absolute molar masses, number average (Mn), weight average (Mw), and dispersity (D = Mw / Mn) can also be calculated. b) Polymer preparation:

[0103] Each sample is solubilized in tetrahydrofuran at a concentration of approximately 1 g / L. The solution is then filtered through a 0.45µm porosity filter before injection. c) SEC 3D Analysis:

[0104] To determine the number-average molar mass (Mn), and where applicable the weight-average molar mass (Mw) and the polydispersity index (Ip) of the polymers, the method below is used.

[0105] The number-average molar mass (Mn), weight-average molar mass (Mw), and polydispersity index of the polymer (hereafter referred to as the sample) are determined in absolute terms by triple-detection size exclusion chromatography (SEC). Triple-detection size exclusion chromatography has the advantage of directly measuring average molar masses without calibration.

[0106] The refractive index increment (dn / dc) of the sample solution is measured online using the peak area detected by the refractometer (RI) of the liquid chromatography equipment. To apply this method, it is essential to ensure that 100% of the sample mass is injected and eluted through the column. The RI peak area depends on the sample concentration, the RI detector constant, and the dn / dc value.

[0107] To determine the average molar masses, the previously prepared and filtered 1 g / L solution is injected into the chromatographic system. The equipment used is a WATERS Alliance chromatographic system. The elution solvent is tetrahydrofuran containing 250 ppm BHT (2,6-diter-butyl 4-hydroxytoluene), the flow rate is 1 mL / min, the system temperature is 35°C, and the analysis time is 60 min. The columns used are a set of three AGILENT columns, commercially known as "PL GEL MIXED B LS". The injected volume of the sample solution is 100 µL. The detection system consists of a Wyatt differential viscometer with the trade name "VISCOSTAR II", a Wyatt differential refractometer with the trade name "OPTILAB T-REX" with a wavelength of 658 nm, and a Wyatt multi-angle static light scattering detector with a wavelength of 658 nm and the trade name "DAWN HELEOS 8+".

[0108] For the calculation of the number-average molar masses and the polydispersity index, the value of the refractive index increment dn / dc of the sample solution obtained above is incorporated. The software used for processing the chromatographic data is Wyatt's ASTRA system. Ozone resistance:

[0109] Ozone resistance measurements were carried out according to ANF ISO 1431-1 (2012) on B15 type FTFT test specimens. The specimens were subjected to an ozone concentration of 50 ppm (parts per hundred million), at a temperature of 40°C, for a duration of up to 14 days, at 10% elongation.

[0110] The test specimens are made from an MFTR plate (called Monsanto), the two ridges at the ends of which serve to hold the specimen in place. Their dimensions are as follows: 78.5mm * 20mm * 1.5mm.

[0111] The appearance of the test specimens was observed under a magnifying glass with a magnification of x5 and was noted according to the terminology described in Annex C of the aforementioned standard, namely: Crack size 0: No cracks; 1: Crack visible under magnification; 2: Crack visible to the naked eye but very small (less than 0.5 mm); 3: Any larger crack; R: Specimen breakage Energy dissipation:

[0112] Rubber compositions were tested under double shear according to ASTM D5992-96 (2011). A double shear test specimen consists of two elastomer discs bonded between three cylindrical metal supports. The bonded discs have a diameter of 8.62 mm (drill diameter).

[0113] The conditions chosen for the dynamic amplitude sweep test are as follows: Test equipment: Metravib DMA + 450 viscoanalyzer, Loading type: single shear, Sample holder type: double shear setup; 3.5 mm gap, Temperature range: ambient (23±2°C), Thermal conditioning: none, Loading frequency: 1 Hz, 95 Hz, Controlled static quantity: none, Controlled dynamic quantity: strain amplitude from ±0.1% to ±100% (forward / reverse), Bonded discs with a diameter of 8.62 mm and a thickness of 2 mm.

[0114] The loss factors tan(δ) reported in Table 1 are derived from the forward curve measured at a strain amplitude of 4% on new specimens at two frequencies, namely 1 Hz and 95 Hz respectively.

[0115] The performance of the loss factor tan(δ) 1Hz is calculated according to the formula: (Loss factor tan(δ) 1Hz control) / (Loss factor tan(δ) 1Hz mixture)*100. A value greater than 100 indicates less dissipation of the mixture and therefore better operation at lower continuous temperatures.

[0116] The performance of the loss factor tan(δ) 95Hz is calculated according to the formula: (Loss factor tan(δ) 95Hz mixture) / (Loss factor tan(δ) 95Hz control)*100. A value greater than 100 reflects a greater energy dissipation of the material and therefore better frequency damping. IV-2 Preparation of compositions

[0117] In the following examples, the rubber compounds were prepared as described in section II-5 above. Specifically, the "non-productive" phase was carried out in a 2.5-liter mixer for 3.5 minutes, at an average paddle speed of 50 rpm, until a maximum drop temperature of 160°C was reached. The "productive" phase was carried out in a roller tool at 23°C for 5 minutes.

[0118] The crosslinking of the composition was carried out at a temperature of 160°C for 50 minutes under pressure. IV-3 Tests of rubber compositions

[0119] The examples presented below are intended to compare the resistance to ozone, and the energy dissipation at 1Hz and 95Hz of two compositions according to the present invention (C1 and C2) with two control compositions (T1 and T2) which differ respectively from the compositions according to the invention only by the nature of the copolymer.

[0120] Table 1 presents the compositions tested (in pieces), as well as the results obtained.

[0121] The loss factor performance results at 1Hz and 95Hz are expressed as a percentage based on 100 relative to the control composition T1 for composition C1 or T2 for composition C2. [Table 1] T1 C1 T2 C2 NR (1) 70 70 EPDM (2) 100 30 EBR (3) 100 30 N550 (4) 30 30 30 30 ZnO (5) 5 5 5 5 Stearic acid (6) 2 2 2 2 TMQ (7) 1 1 1 1 6PPD (8) 1 1 1 1 Anti-ozone wax (9) 2 2 2 2 Peroxide (10) 3 3 3 3 ZDA (11) 4 4 4 4 Ozone Test 0 0 0 0 Performance tan(δ) 1Hz 100 134 100 124 Performance tan(δ) 95Hz 100 97 100 98 (1) Natural rubber (2) EPDM “Keltan 3960Q” from the Lanxess company (3) 80 mol% ethylene-butadiene copolymer of ethylene motifs prepared according to an ethylene and butadiene polymerization process in accordance with Example 4-2 of patent EP 1 954 705 B1 in the name of the Applicants, the polymerization time being adjusted to obtain a molar mass Mn = 153,000 g / mol with a polydispersity index of 1.9 (4) N550 grade carbon black according to ASTM D-1765 (5) Industrial grade zinc oxide from Umicore (6) Stearic acid “Pristerene 4931” from Uniqema (7) 2,2,4-trimethyl-1,2-dihydroquinoline “Pilnox TMQ” from Nocil (8) N-1,3-dimethylbutyl-N-phenylparaphenylenediamine “Santaflex 6-PPD” from Flexsys (9) Antioxidant wax “Cera SER AO 32” from SER Wax Industry (10) 1,3 / 1,4-bis(tert-butylperoxyisopropyl)benzene “Luperox F40” from Arkema (11) Zinc diacrylate (ZDA) “Dymalink SR633” from Cray Valley.

[0122] The results presented in Table 1 above show that the copolymer according to the invention performs as well as EPDM with regard to ozone resistance. However, the compositions according to the invention exhibit lower energy dissipation at 1 Hz, i.e., under typical operating conditions, without significantly impacting energy dissipation at 95 Hz, i.e., under severe operating conditions. Thus, the compositions according to the invention offer a longer service life due to their lower continuous heating while maintaining excellent high-frequency vibration reduction.

Claims

1. Anti-vibration article comprising at least one rubber element that comprises a rubber composition based on at least: - an elastomeric matrix comprising at least one copolymer containing ethylene units and 1,3-diene units, the molar fraction of the ethylene units in the copolymer being within a range extending from more than 50% to 95%, - a reinforcing filler comprising at least one carbon black having a BET specific surface area that is between 5 and 110 m2 / g (measured in accordance with the standard ASTM D6556-10"), - a crosslinking system comprising at least one peroxide and a co-crosslinking agent selected from the group consisting of (meth)acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof, said article being selected from the group consisting of rubber supports, rubber mounts, rubber bushings, rubber pads, rubber bearings, rubber damper pulleys, rubber pipes, rubber plugs and rubber anti-vibration panels.

2. Anti-vibration article according to Claim 1, wherein the copolymer containing ethylene units and 1,3-diene units is a copolymer of ethylene and of 1,3-diene.

3. Anti-vibration article according to either one of the preceding claims, wherein the 1,3-diene units are 1,3-butadiene units.

4. Anti-vibration article according to any one of the preceding claims, wherein the copolymer containing ethylene units and 1,3-diene units is a random copolymer.

5. Anti-vibration article according to any one of the preceding claims, wherein the content of the copolymer containing ethylene units and 1,3-diene units is within a range extending from 30 to 100 phr, preferably from 50 to 100 phr.

6. Anti-vibration article according to any one of the preceding claims, wherein the carbon black has a specific BET of between 10 and 100 m2 / g, preferably between 20 and 80 m2 / g, more preferably between 20 and 70 m2 / g.

7. Anti-vibration article according to any one of the preceding claims, wherein the content of the carbon black is between 20 and 70 phr, preferably within a range extending from 30 to 60 phr.

8. Anti-vibration article according to any one of the preceding claims, wherein the peroxide is an organic peroxide selected from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, n-butyl 4,4'-di(tert-butylperoxy)valerate, OO-(t-butyl) O-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,3(4)-bis(tert-butylperoxyisopropyl)benzene and mixtures thereof, preferably from the group consisting of dicumyl peroxide, n-butyl 4,4'-di(tert-butylperoxy)valerate, OO-(t-butyl) O-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,3(4)-bis(tert-butylperoxyisopropyl)benzene and mixtures thereof.

9. Anti-vibration article according to any one of the preceding claims, wherein the content of peroxide is within a range extending from 0.5 to 10 phr, preferably from 1 to 5 phr.

10. Anti-vibration article according to any one of the preceding claims, wherein the co-crosslinking agent comprises an acrylate derivative of formula (III):         [X]p A     (III) in which: ∘ [X]p corresponds to a radical of formula (IV): in which: • R1, R2 and R3 independently represent a hydrogen atom or a C1-C8 hydrocarbon group selected from the group consisting of alkyl groups which are linear, branched or cyclic, alkylaryl groups, aryl groups and aralkyls, and which are optionally interrupted by one or more heteroatoms, it being possible for R2 and R3 together to form a non-aromatic ring, • (*) represents the point of attachment of the radical of formula (IV) to A, ∘ A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a C1-C30 hydrocarbon group, optionally interrupted and / or substituted by one or more heteroatoms, ∘ A comprising p free valencies, p having a value ranging from 2 to 6, ∘ it being understood that the 2 to 6 X radicals are identical or different.

11. Anti-vibration article according to Claim 10, wherein, in the acrylate derivative of formula (III): ∘ A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a C1-C13 hydrocarbon group, ∘ A comprising p free valencies, p having a value ranging from 2 to 4, ∘ it being understood that the 2 to 4 X radicals are identical or different.

12. Anti-vibration article according to Claim 10 or 11, wherein R1, R2 and R3 represent, independently of one another, a hydrogen atom, a methyl group or an ethyl group.

13. Anti-vibration article according to any one of Claims 10 to 12, wherein A represents an atom selected from the group consisting of Zn, Mg and Fe.

14. Anti-vibration article according to any one of the preceding claims, wherein the content of the co-crosslinking agent is within a range extending from 1 to 20 phr, preferably from 2 to 10 phr.