Rubber composition based on a highly saturated elastomer and a liquid plasticizer

Abstract

The present invention relates to rubber compositions which have improved rolling resistance and improved grip on wet ground. These compositions are based on at least one elastomer matrix comprising at least one copolymer containing ethylene units and 1,3-diene units, wherein the molar fraction of ethylene units in the copolymer is within a range extending from more than 50% to 95%, the copolymer not containing any 1,3-diene units of formula CH2=CR-CH=CH2, the symbol R representing a hydrocarbon chain containing 3 to 20 carbon atoms; a liquid plasticizer comprising from 45% to 100%, by weight, of an unsaturated fatty acid triester of glycerol; more than 30 phr of reinforcing filler and a crosslinking system. The invention also relates to rubber articles comprising a composition according to the invention, in particular pneumatic or nonpneumatic tyres, the tread of which comprises a composition according to the invention.

Description

[0001] RUBBER COMPOSITION BASED ON A HIGHLY SATURATED ELASTOMER AND A LIQUID PLASTICIZER

[0002] The field of the present invention is that of rubber compositions comprising a highly saturated diene elastomer, in particular compositions intended for use in a tire.

[0003] A tire must meet a large number of technical requirements, often contradictory, including low rolling resistance, high wear resistance, and high grip on both dry and wet roads.

[0004] Among these properties, rolling resistance and wear resistance are the most important from an environmental point of view, as they help to reduce fuel consumption and extend the life of the tires, respectively.

[0005] The diene rubber compositions traditionally used in tires are rubber compositions reinforced with highly unsaturated diene elastomers such as polybutadienes, polyisoprenes, butadiene and styrene copolymers. It has been proposed, in particular in document WO 2014 / 114607 A1, to use copolymers of ethylene and 1,3-butadiene in rubber compositions for tires. The rubber compositions reinforced with copolymer of ethylene and 1,3-butadiene are particularly described for improving the performance compromise of a tire, namely wear resistance and rolling resistance.

[0006] However, it is still interesting for tire manufacturers to improve the overall performance compromise, particularly by taking wet grip into account. However, it is known that rolling resistance and wet grip are very often contradictory performances. There is therefore a real need for a solution to improve the performance compromise between rolling resistance and wet grip.

[0007] Continuing its research, the Applicant unexpectedly discovered that the use of a specific liquid plasticizer, combined with a highly saturated copolymer containing ethylene units and 1,3-diene units, makes it possible to simultaneously improve rolling resistance and grip on wet ground. Thus, a first subject of the invention is a rubber composition based on at least:

[0008] - an elastomer matrix comprising at least one copolymer containing ethylene units and 1,3-diene units, the molar fraction of ethylene units in the copolymer being within a range from more than 50% to 95%, the copolymer not containing a 1,3-diene unit of formula CH2=CR-CH=CH2, the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms,

[0009] - a liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol,

[0010] - more than 30 pc of reinforcing filler,

[0011] - a crosslinking system.

[0012] The invention also relates to a rubber article comprising a composition according to the invention, in particular a pneumatic or non-pneumatic tire whose tread comprises a composition according to the invention.

[0013] I- DEFINITIONS

[0014] The expression "based on" used to define the constituents of a catalytic system means the mixture of these constituents, or the product of the reaction of some or all of these constituents with each other.

[0015] The expression "composition based on" means a composition comprising the mixture and / or the in situ reaction product of the different constituents used, some of these constituents being able to react and / or being intended to react with each other, at least partially, during the different phases of manufacture of the composition; the composition can thus be in a totally or partially crosslinked state or in a non-crosslinked state.

[0016] By “elastomer matrix” is meant all the elastomers in the composition, including the copolymer defined below.

[0017] Unless otherwise indicated, the rates of units resulting from the insertion of a monomer into a copolymer are expressed as a molar percentage relative to the total monomer units of the copolymer.

[0018] By the expression "part by weight per hundred parts by weight of elastomer" (or pce), it is meant, within the meaning of the present invention, the part, by mass per hundred parts by mass of the elastomer matrix. On the other hand, any interval of values ​​designated by the expression "between a and b" represents the range of values ​​going from more than a to less than b (that is to say limits a and b excluded) while any interval of values ​​designated by the expression "from a to b" signifies the range of values ​​going from a up to b (that is to say including the strict limits a and b). In the present invention, when an interval of values ​​is designated by the expression "from a to b", the interval represented by the expression "between a and b" is also and preferably designated.

[0019] The compounds mentioned in the description may be of fossil or bio-sourced origin. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. Similarly, the compounds mentioned may also come from the recycling of materials already in use, that is to say, they may be, partially or totally, derived from a recycling process, or obtained from raw materials themselves derived from a recycling process.

[0020] 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).

[0021] II- DESCRIPTION OF THE INVENTION

[0022] II- 1 Elastomer matrix

[0023] According to the invention, the elastomer matrix comprises at least one copolymer containing ethylene units and 1,3-diene units, the ethylene units in the copolymer represent between 50% and 95% by mole of the monomer units of the copolymer, the copolymer not containing a unit of a 1,3-diene of formula CH2=CR-CH=CH2, the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms (hereinafter referred to as "the copolymer").

[0024] By "copolymer containing ethylene units and 1,3-diene units" is meant any copolymer comprising, within its structure, at least ethylene units and 1,3-diene units. The copolymer may thus comprise monomer units other than the ethylene units and the 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 3 to 6 carbon atoms. For example, the alpha-olefin units may be chosen from the group consisting of propylene, butene, pentene, hexene or mixtures thereof. However, the copolymer does not comprise a unit of a 1,3-diene of formula CH2=CR-CH=CH2, the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms.

[0025] As is well known, the expression "ethylene unit" refers to the -(CH2-CH2)- motif resulting from the insertion of ethylene into the elastomer chain.

[0026] As is known, the expression "1,3-diene unit" refers to the 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 a substituted diene such as isoprene for example.

[0027] Preferably, the 1,3-diene units are chosen from the group consisting of butadiene units, isoprene units and mixtures of these 1,3-diene units. In particular, the 1,3-diene units of the copolymer may be 1,3-diene units having 4 to 12 carbon atoms, for example 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene) units. More preferably, the 1,3-diene units are predominantly, in moles, or even preferentially exclusively, 1,3-butadiene units.

[0028] In the copolymer, the ethylene units represent between 50% and 95% by mole of the monomer units of the copolymer. Advantageously, the ethylene units in the copolymer represent between 55% and 90%, preferably from 60% to 90%, preferably from 70% to 85%, by mole of the monomer units of the copolymer.

[0029] Advantageously, the copolymer is a copolymer of ethylene and a 1,3-diene (preferably 1,3-butadiene), that is to say, according to the invention, a copolymer consisting exclusively of ethylene units and 1,3-diene units (preferably 1,3-butadiene). Of course, in accordance with the invention, the 1,3-diene has a formula other than CH2=CR-CH=CH2, the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms.

[0030] 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-membered cyclic unit, 1,2-cyclohexanediyl, of formula (I) as a monomeric unit in the copolymer may result from a series of very specific insertions of ethylene and 1,3-butadiene into the polymer chain during its growth.

[0031] -CH2-CH(CH=CH2)- (II)

[0032] For example, the copolymer of ethylene and a 1,3-diene may be devoid of units of formula (I). In this case, it preferably contains units of formula (II).

[0033] 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 the units of formula (I) and the 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 (eq. 1)

[0034] 0 < o+p < 20 (eq. 2)

[0035] According to the invention, the copolymer, preferably the copolymer of ethylene and a 1,3-diene (preferably 1,3-butadiene), is a random copolymer.

[0036] Advantageously, the number-average mass (Mn) of the copolymer, preferably of the copolymer of ethylene and a 1,3-diene (preferably 1,3-butadiene) is within a range from 100,000 to 300,000 g / mol, preferably from 150,000 to 250,000 g / mol.

[0037] The Mn of the copolymer is determined in a known manner, by size exclusion chromatography (SEC) as described in point III-1.2 below.

[0038] The copolymer can be obtained according to different synthesis methods known to those skilled in the art, in particular depending on the targeted microstructure of the copolymer. Generally, it can be prepared by copolymerization of at least one diene, preferably a 1,3-diene, more preferably 1,3-butadiene, and ethylene and according to known synthesis methods, in particular in the presence of a catalytic system comprising a metallocene complex. Mention may be made, in this respect, of catalytic systems based on metallocene complexes, which catalytic systems are described in documents EP 1 092 731, WO 2004035639, WO 2007054223 and WO 2007054224 in the name of the Applicant. The copolymer, including when it is random, can also be prepared by a process using a preformed type catalytic system such as those described in documents WO 2017093654 Al, WO 2018020122 Al and WO 2018020123 Al.

[0039] The copolymer may consist of a mixture of copolymers containing ethylene units and 1,3-diene units which differ from each other in their microstructures and / or in their macrostructures.

[0040] According to the invention, the elastomer matrix may comprise at least one other diene elastomer, which is not the copolymer as defined above, but this is not necessary. Thus, preferably, the content of the at least one copolymer is within a range from 30 to 100 phr, preferably from 50 to 100 phr, more preferably from 80 to 100 phr. Advantageously, the at least one copolymer containing ethylene units and 1,3-diene units is the only elastomer in the composition, i.e. it represents 100% by mass of the elastomer matrix.

[0041] By "diene" elastomer (or indistinctly rubber), whether natural or synthetic, is meant an elastomer consisting at least in part (i.e., a homopolymer or a copolymer) of diene monomer units (monomers bearing two carbon-carbon double bonds, conjugated or not). This definition includes the copolymer containing ethylene units and 1,3-diene units.

[0042] When the elastomer matrix comprises at least one other diene elastomer, which is not the copolymer containing ethylene units and 1,3-diene units, the at least one other elastomer may be, for example, chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these elastomers. The butadiene copolymers are particularly chosen from the group consisting of butadiene-styrene copolymers (SBR).

[0043] II-2 Plasticizing system

[0044] The rubber composition according to the invention is based on at least one liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol. By definition, a liquid plasticizer is liquid at room temperature (20°C, 1 atm). Advantageously, the fatty acid of the unsaturated fatty acid triester of glycerol comprises from 60% to 100% by weight, more preferably from 70% to 100% by weight, of unsaturated fatty acid triester of glycerol. Particularly advantageously, the unsaturated fatty acid of the unsaturated fatty acid triester is a C12-C22 unsaturated fatty acid (i.e. comprising from 12 to 22 carbon atoms).

[0045] By triester and fatty acid is also meant a mixture of triesters or a mixture of fatty acids, respectively. The fatty acid of the unsaturated fatty acid triester of glycerol preferably comprises more than 60% by weight, more preferably more than 70% by weight, of a C18 unsaturated fatty acid, i.e. chosen from the group consisting of oleic acid, linoleic acid, linolenic acid and mixtures thereof. More preferably, whether of synthetic or natural origin, the fatty acid used comprises more than 60% by weight, more preferably still more than 70% by weight of oleic acid.

[0046] Thus, advantageously, the fatty acid of the unsaturated fatty acid triester of glycerol comprises more than 60% by weight, preferably more than 70% by weight, of a fatty acid chosen from the group consisting of oleic acid, linoleic acid, linolenic acid and mixtures thereof, and even more advantageously more than 60% by weight, preferably more than 70% of oleic acid. Such triesters with a high content of oleic acid are well known; they have been described, for example, in application WO 02 / 088238, as plasticizing agents in tire treads.

[0047] Particularly advantageously, the unsaturated fatty acid triester of glycerol is glycerol trioleate.

[0048] Preferably, the unsaturated fatty acid triester of glycerol is a vegetable oil, preferably a vegetable oil selected from the group consisting of sunflower oil, rapeseed oil and mixtures thereof.

[0049] The Tg of the liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol is advantageously less than -70°C, preferably within a range from -100° to less than -70°C, preferably from -90°C to -75°C.

[0050] The level of the liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol may be within a range of from 5 to 50 phr, preferably from 6 to 40 phr, more preferably from 8 to 30 phr. According to the invention, the composition may comprise a liquid plasticizer other than the liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol, but this is neither obligatory nor preferred.

[0051] When the composition comprises another liquid plasticizer, the total level of liquid plasticizer is preferably within a range of 5 to 150 phr, preferably 10 to 100 phr.

[0052] Preferably, the composition does not comprise a liquid plasticizer other than the liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol or comprises less than 20 phr, preferably less than 10 phr, preferably less than 5 phr. More preferably, the composition does not comprise a liquid plasticizer other than the liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol.

[0053] The composition according to the invention may comprise a hydrocarbon plasticizing resin whose Tg is greater than 20°C, which is by definition a solid at ambient temperature and pressure (20°C, 1 atm).

[0054] Hydrocarbon plasticizing resins are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but which may contain other types of atoms, for example oxygen, which can be used in particular as plasticizing agents or tackifying agents in polymer matrices. They are by nature at least partially miscible (i.e., compatible) at the rates used with the polymer compositions for which they are intended, so as to act as true diluting agents. They have been described for example in the work entitled "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9) of which chapter 5 is devoted to their applications, in particular in pneumatic rubber (5.5. "Rubber Tires and Mechanical Goods").As is known, these hydrocarbon resins can also be described as thermoplastic resins in the sense that they soften upon heating and can thus be molded.

[0055] The softening point of hydrocarbon plasticizing resins is measured according to ISO 4625 ("Ring and Bail" method). The Tg is measured according to ASTM D3418 (1999). The macrostructure (Mw, Mn and Ip) of the hydrocarbon plasticizing resin is determined by size exclusion chromatography (SEC): tetrahydrofuran solvent; temperature 35°C; concentration 1 g / l; flow rate 1 ml / min; solution filtered through a 0.45 pm porosity filter before injection; Moore calibration with polystyrene standards; set of 3 "WATERS" columns in series ("STYRAGEL" HR4E, HR1 and HR0.5); detection by differential refractometer ("WATERS 2410") and its associated operating software ("WATERS EMPOWER").

[0056] Hydrocarbon plasticizing resins can be aliphatic, aromatic, or aliphatic / aromatic, i.e., based on aliphatic and / or aromatic monomers. They can be natural or synthetic, petroleum-based or not (if so, also known as petroleum resins).

[0057] Suitable aromatic monomers include, for example, styrene, alpha-methyl styrene, indene, ortho-, meta-, para-methyl styrene, vinyl toluene, para-tert-butyl styrene, methoxystyrenes, chlorostyrenes, vinyl mesitylene, divinylbenzene, vinyl naphthalene, any vinyl aromatic monomer derived from a C9 fraction (or more generally from a Cx to Cio fraction). Preferably, the vinyl aromatic monomer is styrene or a vinyl aromatic monomer derived from a C9 fraction (or more generally from a Cx to Cio fraction). Preferably, the vinyl aromatic monomer is the minority monomer, expressed as a molar fraction, in the copolymer under consideration.

[0058] Preferably, the hydrocarbon plasticizing resin is selected from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, terpene homopolymer or copolymer resins, C5 cut homopolymer or copolymer resins, C9 cut homopolymer or copolymer resins, alpha-methyl-styrene homopolymer or copolymer resins and mixtures thereof, preferably from terpene copolymer, C5 cut copolymer, C9 cut copolymer resins and mixtures thereof.

[0059] Preferably, the hydrocarbon plasticizing resin has at least one of the following characteristics:

[0060] - a Tg greater than 30°C;

[0061] - a number-average molecular mass (Mn) of between 300 and 2000 g / mol, more preferably between 400 and 1500 g / mol;

[0062] - a polydispersity index (Ip) less than 3, more preferably less than 2 (reminder: Ip = Mw / Mn with Mw average molecular mass by weight).

[0063] More preferably, this hydrocarbon plasticizing resin has all of the above preferred characteristics. The above preferred hydrocarbon plasticizing resins are well known to those skilled in the art and commercially available, for example the polylimonene resins marketed by the company DRT under the name "Dercolyte L120" (Mn=625 g / mol; Mw=1010 g / mol; Ip=1.6; Tg=72°C), or by the company ARIZONA under the name "Sylvagum TR7125C" (Mn=630 g / mol;

[0064] Mw=950 g / mol; Ip=1.5; Tg=70°C); C5 / vinylaromatic cut copolymer resins, in particular C5 / styrene cut or C5 / C9 cut, marketed by Neville Chemical Company under the names "Super Nevtac 78", "Super Nevtac 85" or "Super Nevtac 99", by Goodyear Chemicals under the name "Wingtack Extra", by Kolon under the names "Hikorez T1095" and "Hikorez T1 100", or by Exxon under the names "Escorez 2101" and "Escorez 1273"; and limonene / styrene copolymer resins marketed by DRT under the name "Dercolyte TS 105", or by ARIZONA Chemical Company under the names "ZT115LT" and "ZT5100".

[0065] When included in the composition, the level of plasticizing hydrocarbon resin with a Tg greater than 20°C is within a range of 2 to 200 phr, preferably 2 to 100 phr, preferably 5 to 70 phr, preferably 10 to 50 phr.

[0066] II-3 Reinforcing charge

[0067] The composition according to the invention is based on at least 30 pce of reinforcing filler. A reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.

[0068] The reinforcing filler may comprise carbon black, silica or a mixture thereof. Advantageously, the reinforcing filler of the composition according to the invention comprises more than 50% by mass, preferably more than 80% by mass, of silica.

[0069] The level of reinforcing filler is adjusted by a person skilled in the art depending on the use of the rubber composition. Advantageously, the level of reinforcing filler, in the composition according to the invention, is within a range from 35 to 200 phr, preferably from 40 to 180 phr, preferably from 50 to 160 phr.

[0070] Suitable carbon blacks are all carbon blacks, including those conventionally used in tires or their treads. Among the latter, we will particularly mention the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM D-1765-2017 grades), such as for example blacks NI 15, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772. These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used. Carbon blacks could, for example, already be incorporated into the diene elastomer, in particular isoprene, in the form of a masterbatch (see, for example, applications WO97 / 36724-A2 or W099 / 16600-A1).

[0071] Any type of precipitated silica is suitable as silica, in particular 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, we can notably use the silicas “Ultrasil ® 5000GR”, “Ultrasil ® 7000GR” from the company Evonik, the silicas “Zeosil ® 1085GR”, “Zeosil® 1115 MP”, “Zeosil® 1165MP”, “Zeosil® Premium 200MP”, “Zeosil® HRS 1200 MP” from the company Solvay.As non-HDS silica, the following commercial silicas can be used: silicas “Ultrasil ® VN2GR”, “Ultrasil ® VN3GR” from Evonik, silica “Zeosil® 175GR” from Solvay, silicas “Hi-Sil EZ120G(-D)”, “Hi-Sil EZ160G(-D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210”, “Hi-Sil HDP 320G” from PPG.

[0072] To couple the silica to the diene elastomer, an at least bifunctional coupling agent (or bonding agent) is advantageously used in a well-known manner to ensure a sufficient connection, of a chemical and / or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer. Thus, when the reinforcing filler comprises silica, the composition further comprises at least one agent for coupling the silica to a diene elastomer. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. By "bifunctional", we mean a compound having 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 may comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer. Preferably, the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, marketed under the name “Si69” by the company Evonik or bis-(triethoxysilylpropyl) disulfide, abbreviated to TESPD, marketed under the name “Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl) octanethioate marketed by the company Momentive under the name “NXT Silane”.More preferably, the organosilane is a polysulfurized organosilane.

[0073] When silica is used, the content of coupling agent in the composition of the invention can easily be adjusted by a person skilled in the art. Typically the level of coupling agent represents from 0.5% to 15% by weight relative to the amount of silica.

[0074] II-4 Crosslinking system

[0075] The crosslinking system may be any type of system known to those skilled in the art in the field of tire rubber compositions. It may in particular be based on sulfur, and / or peroxide and / or bismaleimides.

[0076] Preferably, the crosslinking system is sulfur-based, in which case it is referred to as a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or a sulfur-donating agent. At least one vulcanization accelerator is also preferably present. In addition, various known vulcanization activators such as zinc oxide, stearic acid or equivalent compounds such as stearic acid salts and transition metal salts, guanidine derivatives (in particular diphenylguanidine), or even known vulcanization retarders can advantageously be used.

[0077] Sulphur is used at a preferential rate of between 0.3 pce and 10 pce, more preferably between 0.3 and 5 pce. The primary vulcanisation accelerator is used at a preferential rate of between 0.5 and 10 pce, more preferably between 0.5 and 5 pce.

[0078] Any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur may be used as an accelerator, in particular accelerators of the thiazole type and their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate types. Examples of such accelerators include, but are not limited to, the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated as "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N,N-dicyclohexyl-2-benzothiazyl sulfenamide ("DCBS"), N-tert-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-tert-butyl-2-benzothiazyl sulfenimide ("TBSI"), tetrabenzylthiuram disulfide ("TBZTD"), zinc dibenzyldithiocarbamate ("ZBEC") and mixtures of these compounds.

[0079] II-5 Possible additives

[0080] The rubber compositions according to the invention may optionally also comprise all or part of the usual additives usually used in elastomer compositions for tires, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents, etc.

[0081] II-6 Preparation of rubber compositions

[0082] The compositions usable within the framework of the present invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art:

[0083] - a first phase of working or thermomechanical mixing (so-called "non-productive" phase), which can be carried out in a single thermomechanical step during which all the necessary constituents are introduced into a suitable mixer such as a conventional internal mixer (for example of the "Banbury" type), in particular the elastomeric matrix, the reinforcing filler, any other various additives, with the exception of the crosslinking system. The incorporation of the possible filler into the elastomer can be carried out in one or more stages by thermomechanical mixing.In the case where the filler is already incorporated in whole or in part into the elastomer in the form of a masterbatch as described for example in applications WO 97 / 36724 or WO 99 / 16600, it is the masterbatch which is directly mixed and where appropriate the other elastomers or fillers present in the composition which are not in the form of a masterbatch are incorporated, as well as any other various additives other than the crosslinking system. The non-productive phase can be carried out at high temperature, up to a maximum temperature of between 110°C and 200°C, preferably between 130°C and 185°C, for a duration generally of between 2 and 10 minutes.

[0084] - a second phase of mechanical work (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 everything is then mixed for a few minutes, for example between 5 and 15 min.

[0085] Such phases have been described for example in applications EP-A-0501227, EP-A-0735088, EP-A-0810258, WO00 / 05300 or WO00 / 05301.

[0086] The final composition thus obtained is then calendered, for example, in the form of a sheet or plate, in particular for characterization in the laboratory, or else extruded (or co-extruded with another rubber composition) in the form of a semi-finished (or profiled) rubber usable, for example, as a tire tread. These products can then be used for the manufacture of tires, according to techniques known to those skilled in the art.

[0087] 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 in a tire.

[0088] 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 130°C and 200°C, under pressure.

[0089] II-7 Rubber article

[0090] The present invention also relates to a rubber article comprising at least one composition according to the invention. Preferably, the rubber article is chosen from the group consisting of pneumatic or non-pneumatic tires.

[0091] More particularly, the invention also relates to a pneumatic or non-pneumatic tire provided with a tread comprising a composition according to the invention. The composition according to the invention may constitute part or all of the tread of the tire.

[0092] The bandage according to the invention can be intended to equip any type of vehicle, in particular motor vehicles, without any particular limitation.

[0093] III- EXAMPLES

[0094] III- 1 Measurements and tests used

[0095] III- 1.1 Determination of the microstructure of elastomers:

[0096] The microstructure of ethylene and butadiene copolymers is determined by 1H NMR analysis, supplemented by 13C NMR analysis when the resolution of 1H NMR spectra does not allow the attribution and quantification of all species. Measurements are carried out using a BRUKER 500MHz NMR spectrometer at frequencies of 500.43 MHz for proton observation and 125.83MHz for carbon observation. For non-soluble elastomers but having the ability to swell in a solvent, a 4mm z-grad HRMAS probe is used to observe the proton and carbon in proton-decoupled mode. Spectra are acquired at rotation speeds of 4000Hz to 5000Hz. For measurements on soluble elastomers, a liquid NMR probe is used to observe the proton and carbon in proton-decoupled mode.The preparation of insoluble samples is done in rotors filled with the analyzed material and a deuterated solvent allowing swelling, generally deuterated chloroform (CDCL). The solvent used must always be deuterated and its chemical nature can be adapted by the skilled person. 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), generally deuterated chloroform (CDCL). The solvent or solvent blend used must always be deuterated and its chemical nature can be adapted by the skilled person. In both cases (soluble sample or swollen sample): For proton NMR, a single 30° pulse sequence is used. The spectral window is adjusted to observe all the resonance lines belonging to the analyzed molecules.The number of accumulations is adjusted to obtain a sufficient signal-to-noise ratio for the quantification of each pattern. The recycling time between each pulse is adapted to obtain a quantitative measurement. For carbon NMR, a single 30° pulse sequence is used with proton decoupling only during acquisition to avoid “Nuclear Overhauser” (NOE) effects and remain quantitative. The spectral window is adjusted to observe all the resonance lines belonging to the analyzed molecules. The number of accumulations is adjusted to obtain a sufficient signal-to-noise ratio for the quantification of each pattern. The recycling time between each pulse is adapted to obtain a quantitative measurement. NMR measurements are carried out at 25°C.

[0097] III- 1.2 Determination of the macrostructure of polymers by size exclusion chromatography (SEC): a) Principle of measurement:

[0098] 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. Combined with 3 detectors (3D), a refractometer, a viscometer and a 90° light scattering detector, SEC can be used to assess the absolute molar mass distribution of a polymer. The various number-average (Mn), weight-average (Mw) absolute molar masses and the polydispersity (Ip = Mw / Mn) can also be calculated. b) Polymer preparation:

[0099] Each sample is solubilized in tetrahydrofuran at a concentration of approximately 1 g / L. The solution is then filtered through a 0.45 pm porosity filter before injection. c) 3D SEC analysis:

[0100] To determine the number-average molar mass (Mn), and where appropriate the weight-average molar mass (Mw) and the polydispersity index (Ip) of polymers, the method below is used.

[0101] The number-average molar mass (Mn), weight-average molar mass (Mw) and polydispersity index of the polymer (hereinafter referred to as sample) are determined absolutely by triple detection size exclusion chromatography (SEC). Triple detection size exclusion chromatography has the advantage of measuring average molar masses directly without calibration.

[0102] The refractive index increment dn / dc value 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 must be ensured 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.

[0103] To determine the average molar masses, the previously prepared and filtered lg / l solution is used and injected into the chromatographic system. The equipment used is a "WATERS alliance" chromatographic chain. The elution solvent is tetrahydrofuran containing 250 ppm of BHT (2,6-diter-butyl 4-hydroxy toluene), the flow rate is 1 mL.min' 1, the system temperature of 35°C and the analysis time of 60 min. The columns used are a set of three AGILENT columns with the trade name “PL GEL MIXED B LS”. The injected volume of the sample solution is 100 pL. The detection system is composed 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, a Wyatt multi-angle static light scattering detector with a wavelength of 658 nm and the trade name “DAWN HELEOS 8+”.

[0104] 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 integrated. The software for processing the chromatographic data is the “ASTRA de Wyatt” system.

[0105] Fig. 1.3 Determination of Mooney viscosity

[0106] For polymers and rubber compounds, Mooney viscosities ML(l+4) at 100°C are measured using an oscillating consistometer according to ASTM D-1646 (1999). The Mooney plasticity measurement is carried out according to the following principle: the raw compound (i.e. before curing) is molded in a cylindrical chamber heated to 100°C. After one minute of preheating, the rotor rotates within the specimen at 2 revolutions / minute and the torque needed to maintain this movement after 4 minutes of rotation is measured. The Mooney plasticity ML(l+4) is expressed in "Mooney units" (MU, with 1 MU = 0.83 Nm).

[0107] III- 1.4 Dynamic properties

[0108] The dynamic properties tan(ô)max are measured at a temperature of 23 °C on a viscoanalyzer (Metravib VA4000), according to ASTM D 5992-96. The response of a sample of crosslinked composition (cylindrical specimen 4 mm thick and 400 mm 2 of section), subjected to sinusoidal stress in alternating simple shear, at a frequency of 10 Hz, under the defined temperature conditions, for example at 23°C according to standard ASTM D 1349-99. A strain amplitude sweep is carried out from 0.1 to 50% (forward cycle), then from 50% to 0.1% (return cycle). The results used are the loss factor tan(ô). For the return cycle, the maximum value of tan(ô) observed is indicated, noted tan(ô)max at 23°C.

[0109] It is recalled that, in a manner well known to those skilled in the art, the value of tan(ô)max at 23°C is representative of the hysteresis. The tan(ô)max performance results at 23°C are expressed on a base of 100, the value 100 being assigned to the control. A result greater than 100 indicates that the composition of the example considered is less hysteretic at 23°C, reflecting a lower rolling resistance of the tread comprising such a composition.

[0110] Furthermore, the integral property of the tan(ô) value observed from -30°C to 0°C (Int. tan(ô) [-30°C; 0°C]) was also measured on a viscoanalyzer (Metravib VA4000) according to ASTM D5992-96. The response of a crosslinked composition sample (cylindrical specimen with a thickness of 4 mm and a cross-section of 400 m2), subjected to a simple alternating sinusoidal shear stress, at a frequency of 10 Hz, during a temperature scan, under a stationary stress of 0.7 MPa, was recorded. It is recalled that, as is well known to those skilled in the art, the integral of the tan(ô) value observed from -30°C to 0°C is representative of wet grip. The performance results Int. tan(ô) [-30°C; 0°C] are expressed on a base of 100, with the value 100 being assigned to the control. A result above 100 indicates that the composition has better grip on wet ground.

[0111] III-2 Synthesis of copolymer El

[0112] In polymer synthesis, all reagents are obtained commercially except for metallocenes. Butyloctylmagnesium BOMAG (20% in heptane, C = 0.88 mol.L 1 ) comes from Chemtura and is stored in a Schlenk tube under an inert atmosphere. Ethylene, grade N35, comes from Air Liquide and is used without prior purification.

[0113] The copolymer of ethylene and 1,3-butadiene: elastomer E1 (in accordance with the invention) is synthesized according to the procedure described below.

[0114] In a reactor containing methylcyclohexane at 80°C, as well as ethylene (Et) and butadiene (Bd) in the proportions indicated in Table 1, butyloctylmagnesium (BOMAG) is added to neutralize the impurities in the reactor, then the catalytic system (see Table 1). At this point, the reaction temperature is regulated at 80°C and the polymerization reaction starts. The polymerization reaction proceeds at a constant pressure of 8 bar. The reactor is supplied throughout the polymerization with ethylene and butadiene (Bd) in the proportions defined in Table 1. The polymerization reaction is stopped by cooling, degassing the reactor and adding ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered by drying in a vacuum oven to constant mass. The catalytic system is a preformed catalytic system.It is prepared in methylcyclohexane from a metallocene, [Me2SiFlu2Nd(p-BH4)2Li(THF)], a co-catalyst, butyloctylmagnesium (BOMAG), and a preformation monomer, 1,3-butadiene, in the contents indicated in Table 1. It is prepared according to a preparation method in accordance with paragraph II.1 of patent application WO 2017 / 093654 AL.

[0115] The microstructure of copolymer E1 and its properties are shown in Tables 2 and 3. For the microstructure, Table 2 shows the molar ratios of ethylene units (Eth), 1,3-butadiene units, 1,2-cyclohexanediyl units (cycle). [Table 1]

[0116] [Table 2]

[0117] [Table 3]

[0118] III-3 Preparation of compositions

[0119] In the following examples, the rubber compositions were produced as described in point II-6 above. In particular, the “non-productive” phase was carried out in a 0.4 liter mixer for 3.5 minutes, for an average paddle speed of 50 revolutions per minute until a maximum drop temperature of 160°C was reached. The “productive” phase was carried out in a cylinder tool at 23°C for 5 minutes. The crosslinking of the composition was carried out at a temperature of 150°C, under pressure, for a period of 60 minutes.

[0120] III-4 Rubber composition tests

[0121] The examples presented below are intended to compare the rolling resistance and wet grip performance of a composition in accordance with the present invention (Cl) with a control composition (Tl). Table 4 shows the compositions tested (in pce), as well as the results obtained.

[0122] Control composition T1 corresponds to a prior art composition. Composition Cl differs from control composition T1 only by the nature of the liquid plasticizer. [Table 4]

[0123] (1) Elastomer El prepared in point III-2 above

[0124] (2) Silica “Zeosil 1165MP” from Solvay

[0125] (3) Liquid silane triethoxysilylpropyltetrasulfide (TESPT) “Si69” from Evonik (4) Carbon black grade N234 according to ASTM D-1765

[0126] (5) “Escorez 5000 series” resin from Exxon Mobil (Tg = 52°C)

[0127] (6) MES / HPD oil “Catenex SNR” from Shell (Tg = -60°C)

[0128] (7) Glycerol trioleate (sunflower oil with 85% oleic acid by weight) “Lubrirob Tod 1880” from Novance (Tg = -90°C) (8) Diphenylguanidine “Perkacit DPG” from Flexsys

[0129] (9) Anti-ozone wax “VARAZON 4959” from the company Sasol Wax

[0130] (10) Nl,3-dimethylbutyl-N-phenylparaphenylenediamine “Santoflex 6-PPD” from Flexsys

[0131] (11) 2,2,4-trimethyl-l,2-dihydroquinoline “Pilnox TMQ” from Lanxess

[0132] (12) Stearic acid “Pristerene 4931” from Uniqema (13) Industrial grade zinc oxide from Umicore

[0133] (14) N-cyclohexyl-2-benzothiazyl sulfenamide “Santocure CBS” from Flexsys

[0134] The results presented in Table 4 above show that the substitution of a conventional oil of the prior art by a specific liquid plasticizer comprising from 45% to 100% by weight of unsaturated fatty acid triester of glycerol in compositions based on highly saturated diene elastomer, surprisingly makes it possible to improve two contradictory performances, namely rolling resistance and grip on wet ground.

Claims

Claims: 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%, the copolymer not containing any unit of a 1,3-diene of the formula CH2=CR-CH=CH2, the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms, a liquid plasticizer comprising 45% to 100% by weight of glycerol unsaturated fatty acid triester, more than 30 parts per cent of reinforcing filler, and a crosslinking system. A rubber composition according to claim 1, wherein the copolymer containing ethylene units and 1,3-diene units is a copolymer of ethylene and a 1,3-diene. Rubber composition according to any one of the preceding claims, wherein 1,3-diene is 1,3-butadiene.A rubber composition according to any one of the preceding claims, wherein the copolymer containing ethylene units and 1,3-diene units is a statistical copolymer. A rubber composition according to any one of the preceding claims, wherein the proportion of the copolymer containing ethylene units and 1,3-diene units is in the range of 30 to 100 parts per cent, preferably 50 to 100 parts per cent. A rubber composition according to any one of the preceding claims, wherein the fatty acid of the glycerol unsaturated fatty acid triester comprises more than 60% by weight, preferably more than 70% by weight, of a fatty acid selected from the group consisting of oleic acid, linoleic acid, linolenic acid, and mixtures thereof. A rubber composition according to any one of the preceding claims, wherein the glycerol unsaturated fatty acid triester is glycerol trioleate. A rubber composition according to any one of the preceding claims, wherein the glycerol unsaturated fatty acid triester is a vegetable oil, preferably a vegetable oil selected from the group consisting of sunflower oil, rapeseed oil, and mixtures thereof. A rubber composition according to any one of the preceding claims, wherein the proportion of the liquid plasticizer comprising from 45% to 100% by weight of glycerol unsaturated fatty acid triester is in the range of 5 to 50 parts per million, preferably from 8 to 30 parts per million. A rubber composition according to any one of the preceding claims, wherein the reinforcing filler comprises more than 50% by mass, preferably more than 80% by mass, of silica, the composition further comprising at least one coupling agent for silica to a diene elastomer.rubber composition according to any one of the preceding claims, wherein the reinforcing charge ratio is in the range of 35 to 200 pc, preferably from 40 to 180 pc. Rubber composition according to any one of the preceding claims, further comprising from 2 to 100 parts, preferably from 5 to 70 parts, of a hydrocarbon plasticizing resin having a glass transition temperature above 20°C, the hydrocarbon plasticizing resin preferably being selected from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, terpene homopolymer or copolymer resins, C5-cut homopolymer or copolymer resins, C9-cut homopolymer or copolymer resins, alpha-methylstyrene homopolymer or copolymer resins and mixtures thereof.A rubber composition according to any one of the preceding claims, wherein the crosslinking system is a vulcanizing system based on molecular sulfur and / or a sulfur-donating agent. A rubber article comprising a composition as defined in any one of claims 1 to 13. Pneumatic or non-pneumatic tire comprising a composition as defined in any one of claims 1 to 13, said composition preferably being present in the tread of said pneumatic or non-pneumatic tire.

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