EP3380556A1

EP3380556A1 - Rubber composition

Info

Publication number: EP3380556A1
Application number: EP16813013.6A
Authority: EP
Inventors: Etienne Fleury; Anne-Frédérique SALIT; Justin Belz
Original assignee: Compagnie Generale des Etablissements Michelin SCA
Current assignee: Compagnie Generale des Etablissements Michelin SCA
Priority date: 2015-11-27
Filing date: 2016-11-24
Publication date: 2018-10-03
Also published as: WO2017089708A1; US20180346617A1; BR112018010760A8; FR3044316B1; FR3044316A1; CN108350227A; BR112018010760A2

Abstract

The present invention relates to the use of a diene elastomer and a 1,3-dipolar compound in a rubber composition made up of at least one reinforcing filler comprising a reinforcing inorganic filler and a coupling agent, the 1,3-dipolar compound comprising a Q group and an A group connected together by a B group, in which Q comprises a dipole containing at least, and preferably, one nitrogen atom, A comprises an associative group comprising at least one nitrogen atom, and B is an atom or a group of atoms forming a bond between Q and A, the diene elastomer being obtained by stereospecific polymerisation of at least one 1,3-diene by means of a Ziegler-Natta catalytic system and containing less than 150 ppm of the element neodymium. The use of such a diene elastomer and such a 1,3-dipolar compound in the rubber composition makes it possible to ensure very low hysteresis of the rubber composition.

Description

Rubber composition

The present invention relates to diene rubber compositions reinforced with an inorganic filler and used in particular for the manufacture of tires.

In the automotive industry, tires with low rolling resistance or low heating during running are required. The first performance can be sought to reduce fuel consumption, the second to increase the endurance of the tire.

Tires with low rolling resistance or low heat resistance can be achieved by the use of low hysteretic rubber compounds.

Obtaining low hysteretic rubber composition can be done in different ways. One of them is to use coupling agents in the rubber composition that improve the interaction between the elastomer and the reinforcing filler of the rubber composition. Alternatively, it can be used in the rubber composition of the elastomers carrying an interactive function vis-à-vis the reinforcing filler of the rubber composition.

In particular, it is known from patent applications WO 2012/007442 A1 and WO 2014/090756 A1 to use a 1,3-dipolar compound comprising an associative group in a reinforced diene rubber composition to reduce the hysteresis of the composition. of rubber.

The Applicants pursuing their efforts have discovered that the judicious choice of a specific diene elastomer combined with the use of a 1,3-dipolar compound comprising an associative group in an inorganic filler reinforced rubber composition allows a reduction in even more significant hysteresis of the rubber composition.

Thus, an object of the invention is the use of a diene elastomer and a 1,3-dipolar compound in a rubber composition based on at least one reinforcing filler comprising a reinforcing inorganic filler and a coupling agent,

The diene elastomer being obtained by stereospecific polymerization of at least one 1,3-diene by means of a Ziegler-Natta catalytic system and containing less than 150 ppm of the neodymium element.

The 1,3-dipolar compound comprising a group and a group A connected to one another by a group B in which comprises a dipole containing at least and preferably a nitrogen atom, A comprises an associative group comprising at least one minus one nitrogen atom, B is an atom or a group of atoms forming a bond between Q and A.

I. DETAILED DESCRIPTION OF THE INVENTION

In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. The abbreviation "pce" means parts by weight per hundred parts of elastomer (of the total elastomers if several elastomers are present). On the other hand, any range of values designated by the expression "between a and b" represents the range of values greater than "a" and less than "b" (i.e., terminals a and b excluded). while any range of values designated by the term "from a to b" means the range of values from "a" to "b" (i.e. including the strict limits a and b). By the term "composition-based" is meant in the present description a composition comprising the mixture and / or the reaction product in situ of the various constituents used, some of these basic constituents (for example the elastomer, the filler or other additive conventionally used in a rubber composition intended for the manufacture of tire) being capable of, or intended to react with one another, at least in part, during the different phases of manufacture of the composition intended for the manufacture of a tire .

An essential characteristic of the invention is the use of a diene elastomer obtained by stereospecific polymerization of at least one 1,3-diene by means of a Ziegler-Natta catalytic system, and containing less than 150 ppm of the neodymium element

By "diene" elastomer (or indistinctly rubber), one or more elastomers consisting at least in part (ie, a homopolymer or a copolymer) of monomeric diene units (monomers carrying two carbon double bonds) must be understood in known manner. -carbon, conjugated or not).

For the record, stereospecific polymerizations are conducted in the presence of a multi-component catalytic system of Ziegler-Natta type. The catalytic system involves at least three essential organometallic constituents, which are:

a metal precursor based on a metal belonging to one of groups III to VIII;

a metal alkylation agent of the metal precursor, which alkylating agent is based on a Group II or III metal such as Mg or Al;

a halogenating agent, such as an aluminum alkyl halide.

The alkylating agent is also called a cocatalyst. Some catalytic systems use only two components, ie a metal precursor based on a transition metal and a co-catalyst, alkylating agent type.

Those skilled in the art are aware of the conditions for using these three constituents to obtain catalytic systems that are effective for the stereospecific polymerization of conjugated diene (s), as described, for example, in the journal "Neodymium". Based on Ziegler-Natta Catalysts and their Application in Diene Polymerization ", Adv Polym Sci (2006) 204 pp 1-154.

As a metal precursor, mention may be made of compounds based on iron, cobalt, nickel, chromium, titanium, vanadium or a rare earth such as neodymium.

As an alkylating agent, mention may be made of organolithiums, aluminum alkyls or aluminum alkyl hydrides or methylaluminoxanes.

As a halogenating agent, mention may be made of aluminum alkyl halides. Depending on the properties of the diene elastomer to be synthesized which are desired such as its microstructure and its macrostructure and according to the characteristics of the process which are preferred from the point of view of productivity, those skilled in the art choose the constituents of the catalytic system. as well as their relative proportions to obtain a catalytic system which allows under the best conditions the synthesis of the diene elastomer.

The diene elastomer useful for the needs of the invention has the essential characteristic of being obtained by stereospecific polymerization of a 1,3-diene in the presence of a Ziegler-Natta catalytic system. It also has the essential feature of containing less than 150 ppm (parts per million) of neodymium element. In other words, if it contains the neodymium element, whether in metallic form or neodymium derivatives, its content is less than 150 ppm in the diene elastomer. Those skilled in the art understand that the diene elastomer useful for the purposes of the invention is synthesized in the presence of a catalytic system which does not use a neodymium-based metal precursor. According to a particularly preferred embodiment, the diene elastomer useful for the needs of the invention is obtained by stereospecific polymerization of a conjugated diene in the presence of a Ziegler-Natta catalytic system based on titanium. The expression "a titanium catalytic system" is equivalent to saying that the catalytic system contains a titanium-based metal precursor. Those skilled in the art understand that the diene elastomer useful for the purposes of the invention comprises the titanium element preferably in a content of at least 100 ppm, in particular from 100 to less than 1000 ppm of titanium element, which it either in metallic form or titanium derivatives. The presence of the titanium element in the diene elastomer useful for the needs of the invention results from the use of the titanium-based catalyst system in the synthesis of the diene elastomer, Polymerization in the presence of a titanium based catalyst system is well known, and is documented in the Handbook of Polymer Synthesis, Second Edition, H.Kicheldorf, Oskar Nuyken, Graham Swift - 2004 - Technology & Engineering. Of the titanium-based Ziegler-Natta catalytic systems known to catalyze the polymerization of diene, titanium is generally used in the form of a titanium derivative at oxidation state 3 or 4. Among the Ti (III) compounds or Ti (IV) which are suitable in the catalytic system include organooxytitanium or titanium halides, especially titanium tetrachloride.

The Ziegler-Natta catalytic system based on titanium comprises, for example, as cocatalyst an organoaluminium compound which is preferably chosen from AIR ₃ and AIR ₂ H, where R is chosen from alkyl, cycloalkyl, aryl, alkaryl, aralkyl and cycloalkylalkyl radicals. and cycloalkylaryl. Trialkylaluminum compounds or dialkylaluminums are particularly preferred, especially when the alkyl radical is C 2 -C 4.

The catalyst system, in addition to the titanium derivative and the cocatalyst, may comprise a halogenating agent. As a halogenating agent, mention may be made of organoaluminum halides, preferably an XAIR ' ₂ , where R' is chosen from alkyl, cycloalkyl, aryl, alkaryl, aralkyl, cycloalkylalkyl and cycloalkylaryl radicals, X is an atom halogen, preferably an iodine atom.

The polymerization can be carried out according to a continuous or batch process, in bulk, in solution or in dispersion. In a polymerization in the presence of solvent, the solvent is generally chosen from aromatic hydrocarbon solvents, aliphatic and mixtures thereof. As a commonly used solvent, there may be mentioned toluene, pentane, hexane, heptane, cyclohexane and methylcyclohexane.

The monomer polymerized to yield the diene elastomer useful for the purposes of the invention is a diene, preferably a 1,3-diene having from 4 to 8 carbon atoms, more preferably butadiene, isoprene or their mixed.

The relative amounts of monomer, titanium derivatives, cocatalyst and optionally halogenating agent and solvent for the manufacture of the diene elastomer useful for the purposes of the invention are determined by those skilled in the art. depending on the desired characteristics of the diene elastomer such as microstructure and macrostructure, and depending on desired process parameters such as kinetics, yield.

The diene elastomer useful for the purposes of the invention can be synthesized according to any one of the aforementioned variants of system-catalyzed polymerization. Ziegler-Natta catalyst based on titanium. The diene elastomer useful for the purposes of the invention may be a mixture of diene elastomers which differ from each other by their microstructure or their macrostructure. According to one embodiment of the invention, the diene elastomer useful for the purposes of the invention contains more than 90 mol% 1,4-cis bond.

According to one particular embodiment of the invention, the diene elastomer that is useful for the purposes of the invention is a polyisoprene, preferably a polyisoprene said to have a high cis content, that is to say greater than 90 mol%. 1,4-c / s linkage. For example, commercial polyisoprenes such as Nippon Zeon's NI POL 2200 are suitable.

Another essential feature of the invention is the use of a 1,3-dipolar compound.

The 1,3-dipolar compound comprises one (one or more) group Q and one (one or more) group A connected to each other by a group B in which:

Q. comprises a dipole containing at least one and preferably a nitrogen atom, A comprises an associative group comprising at least one nitrogen atom,

- B is an atom or a group of atoms forming a bond between Q. and A.

According to any of the embodiments of the invention, the 1,3-dipolar compound preferably contains a single Q. group connected to the group (s) A by the group B. According to any one of the In embodiments of the invention, the 1,3-dipolar compound more preferably contains a single group Q and a single group A connected to each other by group B.

By dipole is meant a function capable of forming a dipolar cycloaddition [1,3] on an unsaturated carbon-carbon bond.

By "associative group" is meant groups capable of associating with each other by hydrogen bonds, each associative group comprising at least one "site" donor and one acceptor site vis-à-vis the hydrogen bond so that two identical associative groups are self-complementary and can associate with each other forming at least two hydrogen bonds.

According to a particular embodiment of the invention, the group A is selected from the group consisting of imidazolidinyl, triazolyl, triazinyl, bis-ureyl and ureidopyrimidyl groups. According to a preferred embodiment of the invention, group A corresponds to one of the following formulas (I) to (V):

or :

Ch denotes a carbon chain which may optionally contain heteroatoms,

- * represents a direct attachment to B,

R denotes a hydrocarbon group which may optionally contain heteroatoms,

X denotes an oxygen or sulfur atom, or an NH group, preferably an oxygen atom.

Generally, the ring in formula (I) is a 5- or 6-membered ring.

According to a more preferred embodiment of the invention, the group A corresponds to the formula (VI) where * represents a direct attachment to B.

Group B which is an atom or a group of atoms forming a bond between Q. and A is preferably a group containing up to 20 carbon atoms and may contain at least one heteroatom. B may be an aliphatic chain preferably containing 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms, or a group containing an aromatic unit and preferably containing 6 to 20 carbon atoms. more preferably 6 to 12 carbon atoms. According to a preferred embodiment of the invention, the 1,3-dipolar compound is selected from the group consisting of nitrile oxides, nitrones and nitriles imines, in which case Q. contains a -C≡N → 0 unit , -C = N (→ 0) - or -C≡N → N.

According to the particular embodiment of the invention wherein Q. comprises a -C≡N-> 0 unit, Q preferably denotes the unit corresponding to formula (VII) in which four of the five identical symbols R ₄ to R ₈ or different, are each an atom, in particular H, or a group of atoms and the fifth symbol designates a direct attachment to B, knowing that R ₄ and R ₈ are preferably both different from H. The group of Atoms are preferably an aliphatic group or a group containing one (or more) aromatic units. The aliphatic group may contain 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms. The group containing one (or more) aromatic unit may contain 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.

R ₄ , R ₆ and R ₈ are each preferably an alkyl group of 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, more preferably a methyl or ethyl group. According to a variant of this particular embodiment of the invention, R ₄ , R ₆ and R ₈ are identical. According to this variant in which they are identical, R ₄ , R ₆ and R ₈ are each preferably an alkyl group of 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, even more preferably a methyl or ethyl group.

According to another variant of this particular embodiment of the invention according to which Q denotes the unit of formula (VII), B represents a unit chosen from - (CH ₂ ) yi-, - [NH- (CH ₂ ) y ₂ ] xi- and - [O- (CH 2) y ₃ ] x ₂ -, y ₁ , y ₂ and y ₃ independently represent an integer from 1 to 6, and x _x and x ₂ independently represent a integer ranging from 1 to 4. This variant can be combined with the variant according to which R ₄ , R ₆ and R ₈ are identical, preferably each an alkyl group of 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. carbon, more preferably a methyl or ethyl group.

The 1,3-dipolar compound is advantageously one of the compounds of formula (VIII) to (XIII)

(XI I) (XI I I)

More preferably, the 1,3-dipolar compound is the compound of formula (VI II), 2,4,6-trimethyl-3- (2- (2-oxoimidazolidin-1-yl) ethoxy) benzonitriloxide.

According to the particular embodiment of the invention wherein Q. comprises a -C = N (-> O) - motif, Q preferably comprises the unit corresponding to formula (XIV) or (XV)

or :

Yi is an aliphatic group, preferably an alkyl group preferably containing 1 to 12 carbon atoms, or a group containing 6 to 20 carbon atoms and having an aromatic unit, preferably an aryl or alkylaryl group, more preferably a phenyl or tolyl group ,

and Y ₂ is an aliphatic group, preferably a saturated hydrocarbon group preferably containing 1 to 12 carbon atoms, or a group comprising an aromatic unit and preferably containing 6 to 20 carbon atoms, Y ₂ having a direct attachment to B. According to this particular embodiment of the invention, the 1,3-dipolar compound is one of the 1,3-dipolar compounds of formula (XVI) to (XX):

(XIX) (XX) with Yi being as defined above, namely an aliphatic group, preferably an alkyl group preferably containing 1 to 12 carbon atoms, or a group containing 6 to 20 carbon atoms and having an aromatic unit preferably an aryl or alkylaryl group, more preferably a phenyl or tolyl group.

The level of 1,3-dipolar compound used is expressed as the molar equivalence value of group A. For example, if the 1,3-dipolar compound contains a single group A as for example in the compound of formula (VII I), at one mole of 1,3-dipolar compound corresponds to one mole of group A. If the 1,3-dipolar compound contains two groups A, one mole of 1,3-dipolar compound corresponds to two moles of group A. In the latter case the use of the 1,3-dipolar compound according to a molar equivalent of group A corresponds to one half-mole of 1,3-dipolar compound.

According to any of the embodiments of the invention, the amount of 1,3-dipolar compound used is preferably from 0.01 to 50, more preferably from 0.01 to 10, even more preferably from 0.03 to 5, more preferably from 0.03 to 3 molar equivalents of group A per 100 moles of monomeric units constituting the diene elastomer useful for the needs of the invention. The preferred ranges can be applied to any of the embodiments of the invention.

According to a particular embodiment of the invention, the 1,3-dipolar compound is pre-grafted onto the diene elastomer useful for the purposes of the invention. In other words, the diene elastomer useful for the purposes of the invention can be modified by grafting the 1,3-dipolar compound before it is introduced into the rubber composition.

According to this particular embodiment of the invention, the diene elastomer useful for the needs of the invention is modified after graft polymerization of the 1,3-dipolar compound. The grafting of the 1,3-dipolar compound is carried out by [3 + 2] cycloaddition of the reactive group (s) of the 1,3-dipolar compound on one or more double bonds of the chains of the diene elastomer. The mechanism of the cycloaddition of a nitrile oxide, a nitrone and a nitrile imine can be illustrated by the following equations, in which the symbol H represents any substituent:

Cycloaddition of a nitrile oxide on an unsaturation or double bond of a diene elastomer (here a polyisoprene)

Cycloaddition of a nitrone on an unsaturation or double bond of a diene elastomer (here a polyisoprene)

Cycloaddition of a nitrile imine on an unsaturation or double bond of a diene elastomer (here a polyisoprene)

The grafting of the 1,3-dipolar compound on the diene elastomer useful for the needs of the invention can be carried out in bulk or in solution, preferably in bulk.

The mass grafting of the 1,3-dipolar compound on the diene elastomer useful for the purposes of the invention can be carried out in an internal mixer or an external mixer such as a roll mill. The grafting is then carried out either at a temperature of the external mixer or the internal mixer below 60 ° C., followed by a grafting reaction step in a press or in an oven at temperatures ranging from 80 ° C. to 200 ° C. or at a temperature of the external mixer or internal mixer greater than 60 ° C without subsequent heat treatment. When the grafting is carried out in bulk, it is preferably carried out in the presence of an antioxidant.

The solution grafting of the 1,3-dipolar compound on the diene elastomer useful for the purposes of the invention may be carried out continuously or discontinuously after the synthesis of the diene elastomer by Ziegler Natta polymerization based on titanium. The diene elastomer thus grafted can be separated from its solution by any type of means known to those skilled in the art and in particular by a stripping operation with steam. The rubber composition in which the diene elastomer useful for the purposes of the invention and the 1,3-dipolar compound are used contains a reinforcing filler and a coupling agent, which reinforcing filler comprises a reinforcing inorganic filler.

The reinforcing filler is any type of so-called reinforcing filler, known for its ability to reinforce a rubber composition that can be used for manufacturing tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, which is associated in a known manner a coupling agent, or a mixture of these two types of load.

Such a reinforcing filler typically consists of nanoparticles whose average size (in 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.

Suitable carbon blacks are all carbon blacks, especially blacks conventionally used in tires or their treads (so-called pneumatic grade blacks). Among the latter, there will be mentioned more particularly the reinforcing carbon blacks of the series 100, 200, 300, or the series blacks 500, 600 or 700 (ASTM grades), such as, for example, the blacks N115, 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.

"Reinforcing inorganic filler" means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called "white" filler, "clear" filler or even "non-black" filler. as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other words able to replace, in its function reinforcement, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.

Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, preferentially silica (SiO ₂ ). The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m ² / g, preferably from 30 to 400 m ² / g, especially between 60 and 300 m ² / g-A highly dispersible precipitated silica (so-called "HDS"), include for example the silicas "Ultrasil" 7000 and "Ultrasil" 7005 from the company Evonik-Degussa, the silicas "Zeosil" 1165MP, 1135MP , 1115MP and Premium 200MP from Rhodia, the "Hi-Sil" silica EZ150G from PPG, the "Zeopol" silicas 8715, 8745 and 8755 from Huber, the high surface area silicas as described in the application WO 03/016387.

In the present disclosure, the BET surface area is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" Vol. 60, page 309, February 1938, specifically according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: time at 160 ° C - relative pressure range p / po: 0.05 at 0.17). The CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).

The physical state under which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules or beads. Of course, reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas as described above.

Those skilled in the art will understand that as an equivalent load of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular an organic filler such as carbon black, since this filler reinforcing would be covered with an inorganic layer such as silica, or would comprise on its surface functional sites, including hydroxyl, requiring the use of a coupling agent to establish the connection between the filler and the elastomer. By way of example, mention may be made, for example, of carbon blacks for tires as described for example in documents WO 96/37547 and WO 99/28380.

According to a particular embodiment of the invention, the inorganic filler, preferably a silica, represents more than 50% by weight of the reinforcing filler of the rubber composition. It is said that the reinforcing inorganic filler is the majority.

When combined with a predominant reinforcing inorganic filler such as silica, the carbon black is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.5 and 20 phr, in particular between 2 and 20 phr). and 10 phr). In the intervals indicated, the coloring properties are black pigmentation) and anti-UV carbon blacks, without otherwise penalizing the typical performance provided by the reinforcing inorganic filler.

The total reinforcing filler content is preferably between 20 and 200 phr. Below 20 phr, reinforcement of the rubber composition may be insufficient to provide an adequate level of cohesion or wear resistance of the rubber compound of the tire comprising this composition. Beyond 200 phr, there is a risk of increasing the hysteresis and therefore the rolling resistance of the tires. For this reason, the total reinforcing filler content is more preferably between 30 and 150 phr, more preferably 50 to 150 phr, especially for use in a tire tread. Any of these total reinforcing charge ratio ranges can be applied to any of the embodiments of the invention. In order to couple the reinforcing inorganic filler to the diene elastomer useful for the needs of the invention, a coupling agent is used in a well-known manner, in particular an at least bifunctional silane (or bonding agent) intended to ensure a sufficient connection, of chemical and / or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer. In particular, organosilanes or at least bifunctional polyorganosiloxanes are used.

In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described for example in the applications WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650).

In particular, polysulphide silanes having the general formula (V) are not suitable for limiting the definition below.

Z - G - S _x - G - Z (V)

in which :

x is an integer of 2 to 8 (preferably 2 to 5);

- the symbols G, which are identical or different, represent a divalent hydrocarbon group (preferably an alkylene group having ₈ or Ci arylene C ₆ -C _2, more particularly alkylene Ci-Ci _0, in particular Ci-C ₄ , especially propylene);

the symbols Z, identical or different, correspond to one of the three formulas below: in which:

- the radicals R ^1, substituted or unsubstituted, identical or different, represent an alkyl group _Ci-8 cycloalkyl, C ₅ -C ₈ aryl or C ₆ -C ₈ (preferably alkyl groups -C ₆ , cyclohexyl or phenyl, especially C ₁ -C ₄ alkyl groups, more particularly methyl and / or ethyl).

- the radicals R ^2, substituted or unsubstituted, identical or different, represent an alkoxy group or Ci-Ci ₈ cycloalkoxy, C ₅ -C ₈ (preferably a group selected from alkoxyls and C ₈ cycloalkoxyls C ₅ -C ₈ , more preferably still a group selected from C ₁ -C ₄ alkoxyls, in particular methoxyl and ethoxyl).

In the case of a mixture of polysulfurized alkoxysilanes corresponding to formula (I) above, in particular common commercially available mixtures, the average value of "x" is a fractional number preferably of between 2 and 5, more preferably close to 4. But the invention can also be advantageously implemented for example with disulfide alkoxysilanes (x = 2).

By way of examples of polysulphide silanes, mention may be made more particularly of bis (C ₁ -C ₄ ) alkoxy-C ₁ -C ₄ alkylsilyl-C ₁ -C ₄ alkyl (especially disulfide, trisulphide or tetrasulfide) polysulphides. )), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C 2 H ₅ O) ₃ Si (CH 2) 3 S 2] 2 or bis (triethoxysilylpropyl) disulfide, in abbreviated form, is especially used. TESPD, of formula [(C2H ₅ 0) ₃ Si (CH2) 3S] 2. As coupling agent other than polysulfurized alkoxysilane, there may be mentioned in particular bifunctional POSS (polyorganosiloxanes) or hydroxysilane polysulfides as described in patent applications WO 02/30939 (or US Pat. No. 6,774,255), WO 02 / 31041 (or US 2004/051210) or silanes or POSS bearing azodicarbonyl functional groups, as described for example in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534.

According to any one of the embodiments of the invention, the coupling agent may be one of the silanes mentioned. The content of coupling agent is advantageously less than 30 phr, it being understood that it is generally desirable to use as little as possible. Typically the level of coupling agent is from 0.5% to 15% by weight relative to the amount of inorganic filler. Its content is preferably between 0.5 and 16 phr, more preferably in a range from 3 to 10 phr. This level is easily adjusted by those skilled in the art according to the level of inorganic filler used in the composition. The rubber composition may also contain, in addition to the coupling agents, coupling activators, inorganic filler agents or, more generally, processing aids which can be used in a known manner, by means of an improvement of the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state.

According to any of the embodiments of the invention, the rubber composition may further contain a chemical crosslinking agent. Chemical crosslinking allows the formation of covalent bonds between the elastomer chains. The chemical crosslinking agent may be a vulcanization system or one or more peroxide compounds. According to a first variant, the vulcanization system itself is based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator. To this basic vulcanization system are added, incorporated during the first non-productive phase and / or during the production phase as described later, various known secondary accelerators or vulcanization activators such as zinc oxide. stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine). Sulfur is used at a preferential rate of 0.5 to 12 phr, in particular from 1 to 10 phr. The primary vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5 phr. These preferred ranges can be applied to any of the embodiments of the first variant of the invention. As accelerator (primary or secondary) can be used any compound capable of acting as an accelerator of vulcanization of diene elastomers in the presence of sulfur, in particular thiazole-type accelerators and their derivatives, accelerators of thiuram type, zinc dithiocarbamates. Preferably, a primary accelerator of the sulfenamide type is used.

According to a second variant, when the chemical crosslinking is carried out using one or more peroxide compounds, the said peroxide compound (s) represent from 0.01 to 10 phr. As peroxidic compounds that can be used as chemical crosslinking systems, mention may be made of acyl peroxides, for example benzoyl peroxide or p-chlorobenzoyl peroxide, peroxide ketones, for example methyl ethyl ketone peroxide or peroxyesters, for example butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxyphthalate, alkyl peroxides, for example dicumyl peroxide, di-t-butyl peroxybenzoate and 1,3-bis (t-butyl peroxyisopropyl) benzene, hydro peroxides, for example, t-butyl hydroperoxide. The rubber composition may also comprise all or part of the usual additives usually used in elastomer compositions intended to constitute external mixtures of finished articles of rubber such as tires, in particular treads, such as plasticizers for example or extension oils, whether these are of aromatic or non-aromatic nature, especially very low or non-aromatic oils (eg, paraffinic oils, hydrogenated naphthenics, MES or TDAE oils), vegetable oils, in particular glycerol esters such as glycerol trioleates, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, reinforcing resins (such as resorcinol or bismaleimide), acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M) as described by way of example in WO 02/10269.

The rubber composition may further contain a second diene elastomer other than the diene elastomer useful for the purposes of the invention.

The second diene elastomer is a conventional diene elastomer in the field of tires such as elastomers chosen from polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, copolymers of isoprene and mixtures of these elastomers.

It will be noted that the improvement in the properties of the rubber composition will be all the greater, as the proportion of the second diene elastomer in the rubber composition will be smaller. Therefore, the diene elastomer useful in the requirements of the invention, in pre-grafted form or not, is present in the rubber composition preferably in an amount greater than 50 phr, more preferably greater than 75 phr. even more preferably greater than 90 phr. These preferred ranges can be applied to any of the embodiments of the invention.

The rubber composition can be manufactured in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes referred to as "non-phase" phase). at high temperature, up to a maximum temperature of between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C, followed by a second mechanical working phase (sometimes referred to as a "productive" phase). ") at a lower temperature, typically below 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the chemical crosslinking agent, in particular the vulcanization system. In general, all the basic constituents of the composition included in the tire of the invention, with the exception of the chemical crosslinking agent, are intimately mixed by thermomechanical mixing, in one or more steps up to reaching the maximum temperature of between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C.

By way of example, the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible setting agents, are introduced into a suitable mixer such as a conventional internal mixer. complementary additives and other miscellaneous additives, with the exception of the chemical crosslinking agent. The total mixing time in this non-productive phase is preferably between 1 and 15 minutes. After cooling the mixture thus obtained during the first non-productive phase, the chemical crosslinking agent is then incorporated at low temperature, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.

In the particular case where the 1,3-dipolar compound is pre-grafted onto the diene elastomer useful for the needs of the invention, it is the diene elastomer in its grafted form which is introduced into the appropriate mixers. In other cases, the diene elastomer useful for the purposes of the invention and the 1,3-dipolar compound are introduced as such as basic constituents in the appropriate mixers. In these other cases, the 1,3-dipolar compound is preferably thermomechanically kneaded with the diene elastomer useful for the purposes of the invention before introducing the other basic constituents of the rubber composition.

The final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded in the form of a rubber profile that can be used as a semi-finished tire for vehicle.

The rubber composition, which can be either in the green state (before crosslinking or vulcanization), or in the fired state (after crosslinking or vulcanization), can be a semi-finished product that can be used in a tire, particularly as a tire tread.

The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation. II. EXAMPLES OF THE INVENTION 11. Measurements and Tests Used: ll. Measurement of the Levels of Neodymium or Titanium Derivatives

Any diene elastomer synthesized in the presence of a catalyst system comprising a metal precursor may contain the metallic element in the metal form or derivatives of this metal. To quantify in the elastomer the content of the metallic element, whether in the form of metal or metal derivatives, is used an indirect method that uses the mineralization of a sampling of the elastomer and atomic emission spectrometry by induced plasma coupling. This method makes it possible to determine the nature and the mass content of the metallic element present in the mineralized sample. This measured content is also the mass content in the metal element in the sample of non-mineralized elastomer. The mass content of the metal element whether it is in the form of metal or metal derivatives in the elastomer is therefore expressed in part per million (ppm) of the neodymium element. Thus, at a content of 100 ppm of Nd element measured in the mineralized elastomer sample corresponds to 100 ppm of Nd element in the non-mineralized elastomer. The method is described in detail below:

Induced Plasma Coupled Atomic Emission Spectrometry (ICP-AES) is a technique for performing both qualitative and quantitative elemental analysis.

The determination of the level of catalytic residues by ICP-AES is broken down into two steps: the mineralization of the sample (dissolve the elements of the sample) and the analysis of the solution obtained by ICP-AES.

The mineralization of the sample consists of acid digestion assisted by microwaves. A sample of several tens of mg of sample is cut into small pieces and placed in a microwave reactor with a concentrated mixture of nitric and hydrochloric acids (the nitric acid must be in excess and the composition of the mixture may vary from 60/40 to 90/10% v: v). The reactor is closed and placed in a microwave oven where it undergoes a program of mineralization: the microwaves rotate the polar molecules causing a heating by molecular friction and a release of heat in the heart of the mass. Under the effect of temperature and pressure (temperature range up to 220 ° C and maximum pressure of 75bar, temperature dependent), the material oxidizes and the elements go into solution. The solution is then transferred quantitatively into a volumetric flask of known volume and analyzed by ICP-AES.

The ICP-AES technique (gas: Argon, plasma power: 1100W, emission wavelengths λ-ρ = 334.941nm and ANCI = 401.225nm) uses a plasma to desolate, vaporize, atomize (sometimes ionize) and excite the elements of the sample solution. When excited atoms or ions return to their ground state, they emit a length characteristic of the element and whose intensity is proportional to the concentration of the element in the solution. By comparing the emission line intensities of the Ti and Nd elements to an external calibration range, the concentration of these elements in the sample can be determined.

11.1.2- Microstructure of elastomers:

The microstructure is determined according to the method described in the article entitled "Fast and robust method for the determination of microstructure and composition in butadiene, styrene-butadiene, and isoprene rubber by near-infrared spectroscopy", Vilmin F., Dussap C, Coste N., Appl Spectrosc. 2006; 60 (6): 619-30.

11.1.3- Mooney Plasticity:

To measure the Mooney plasticity, an oscillating consistometer is used as described in the French standard NF T 43-005 (1991). The Mooney plasticity measurement is carried out according to the following principle: the raw composition (i.e., before firing) is molded in a cylindrical chamber heated to 100 ° C. After one minute of preheating, the rotor rotates within the test tube at 2 revolutions / minute and the useful torque is measured to maintain this movement after 4 minutes of rotation. Mooney plasticity (ML 1 + 4) is expressed in "Mooney unit" (UM, with 1 MU = 0.83 Newton meter).

11.1.4- Dynamic properties:

Dynamic properties are measured on a viscoanalyzer (Metravib VA4000) according to ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical specimen 4 mm in thickness and 400 mm ² in section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, is recorded under normal conditions. temperature (23 ° C) and at 60 ° C according to ASTM D 1349-99. A strain amplitude sweep is performed from 0.1% to 100% (forward cycle) and then from 100% to 0.1% (return cycle). The results used are the loss factor tan (δ) at 23 and 60 ° C. For the return cycle, the maximum value of tan (δ) observed, denoted tan (δ) max, is indicated. The results are reported in base 100 relative to a reference. The lower the value, the lower the value of tan (δ) max, the better the gain in hysteresis.

II.2-Preparation of the rubber compositions:

The IR-Ti and IR-Nd elastomers are used for the preparation of the C1 and C2 rubber compositions.

IR-Ti is a commercial polyisoprene, the "NIPOL2200" from Nippon Zeon, a polyisoprene prepared by Ziegler Natta polymerization in the presence of a Ti-based catalyst system. IR-Nd is a polyisoprene prepared by Ziegler Natta polymerization in the presence of a neodymium-based catalyst system as described in application WO 2014086804. It contains more than 150 ppm of the Nd element. dipolar used is 2,4,6-trimethyl-3- (2- (2-oxoimidazolidin-1-yl) ethoxy) benzonitriloxide, the synthesis of which is described in patent application WO 2012007442.

The formulations (in phr) of compositions Cl, Cl-R, C2 and C2-R are described in Table 1.

Only Cl is a composition which corresponds to a use according to the invention, since it results from the use of the 1,3-dipolar compound and IR-Ti.

The composition Cl-R differs from the composition C1 in that it is free of 1,3-dipolar compound. The composition C2 differs from Cl by the origin of the elastomer, since in C2 is used IR-Nd. The composition C2-R is a composition which is devoid of compound

I, 3-dipolar and which contains IR-Nd.

The rubber compositions are prepared in the following manner:

the diene elastomer, optionally the 1,3-dipolar compound, is introduced into an internal Polylab mixer 85 cm ³ , 70% filled and having an initial tank temperature of approximately 50.degree.

thermomechanical work is carried out for 1 to 2 minutes at 110 ° C.

then the reinforcing filler, the coupling agent, the various other ingredients with the exception of the vulcanization system are introduced,

- then thermomechanical work (non-productive phase) is carried out in one step

(total mixing time equal to about 5 minutes) until reaching a maximum "falling" temperature of 160 ° C,

the mixture thus obtained is recovered, cooled and the vulcanization system (sulfur and accelerator) is added to an external mixer (homo-finisher) at 25 ° C., mixing the whole (productive phase) for about 5 to 6 minutes. .

II.3-Bake properties of rubber compositions: The compositions after vulcanization are calendered, either in the form of plates (thicknesses ranging from 2 to 3 mm) or thin sheets of rubber, for the measurement of their physical properties or mechanical, either in the form of directly usable profiles, after cutting and / or assembly to the desired dimensions, for example as semi-finished products for tires, in particular for treads. The results are shown in Table 2. C1-R and C2-R are reference compositions for evaluating the gain in hysteresis by the combined use of the 1,3-dipolar compound and IR respectively and IR-Nd. Therefore, the values of tan (δ) max of Cl-R and C2-R are equal to 100 and are to be compared to the respective values of tan (δ) max of Cl and C2.

It is observed that Cl has values of tan (δ) max at 23 ° and 60 ° C are respectively 55 and 59, against only 67 and 75 for C2. These values show that the decrease in the tan (δ) max value at 23 and 60 ° C is much higher when using IR-Ti than IR-Nd in combination with the 1,3-dipolar compound.

These unexpected results indicate that the highest hysteresis gain is obtained when the 1,3-dipolar compound and a diene elastomer synthesized by Ziegler-Natta polymerization are used in the rubber composition in the presence of a catalytic converter system. titanium base.

Table 1

1) "NIPOL2200" from Nippon Zeon, IR synthesized by Ziegler Natta polymerization of isoprene in the presence of a Ti-based catalyst system

2) IR synthesized by Ziegler Natta polymerization of isoprene in the presence of an Nd-based catalytic system

3) N234

4) Silica "Zeosil 1165 MP" Rhodia company in the form of microbeads

5) TESPT ("Si69" company Degussa)

6) 2,4,6-trimethyl-3- (2- (2-oxoimidazolidin-1-yl) ethoxy) benzonitriloxide

7) N-cyclohexyl-2-benzothiazyl sulfenamide ("Santocure CBS" Flexys company).

Table 2

Cl-R C2 C2 R cooking properties

Tano 23 ° C 55 100 67 100

Tanô _max 60 ° C 59 100 75 100

Claims

claims

1. Use of a diene elastomer and a 1,3-dipolar compound in a rubber composition based on at least one reinforcing filler comprising a reinforcing inorganic filler and a coupling agent,

the 1,3-dipolar compound comprising a group Q and a group A connected to each other by a group B in which Q comprises a dipole containing at least and preferably a nitrogen atom, A comprises an associative group comprising at least a nitrogen atom, B is an atom or a group of atoms forming a bond between Q. and A, characterized in that

the diene elastomer is obtained by stereospecific polymerization of at least one 1,3-diene by means of a Ziegler-Natta catalyst system and contains less than 150 ppm of the neodymium element.

2. Use according to claim 1 wherein the diene elastomer is obtained by stereospecific polymerization of a conjugated diene in the presence of a titanium-based Ziegler-Natta catalyst system.

3. Use according to any one of claims 1 to 2 wherein the diene elastomer comprises from 100 to less than 1000 ppm of titanium element.

4. Use according to claim 1 to 3 wherein the diene elastomer, preferably a polyisoprene, contains more than 90% 1,4-cis bond.

5. Use according to any one of claims 1 to 4 wherein the 1,3-dipolar compound is pre-grafted on the diene elastomer.

Use according to any one of claims 1 to 5 wherein the group A is selected from the group consisting of imidazolidinyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups.

7. Use according to any one of claims 1 to 6 wherein the group A corresponds to one of the following formulas (I) to (V), preferably to the formula (VI):

HN. NOT- *

(D

or :

Ch denotes a carbon chain which may optionally contain heteroatoms,

- * represents a direct attachment to B,

R denotes a hydrocarbon group which may optionally contain heteroatoms,

X denotes an oxygen or sulfur atom, or an NH group, preferably an oxygen atom.

8. Use according to any one of claims 1 to 7 wherein the compound

1,3-dipolar is selected from the group consisting of nitrile oxides, nitrones and nitriles imines.

Use according to any one of claims 1 to 8 wherein Q contains -C≡N-> 0, preferably refers to the unit of formula (VII)

in which :

four of the five symbols R ₄ to R ₈ , which may be identical or different, are each an atom or a group of atoms which is preferably an aliphatic group or a group containing an aromatic unit and the fifth symbol denotes a direct attachment to B, given that R ₄ and R ₈ are preferably both different from H.

10. Use according to claim 9 wherein R ₄ , R ₆ and R ₈ are each an alkyl group of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

11. Use according to any one of claims 9 to 10 wherein R ₄ , R ₆ and R ₈ are each methyl or ethyl.

12. Use according to any one of claims 9 to 11 wherein Q denotes the unit of formula (VII) defined in any one of claims 9 to 11, B represents a unit selected from - (CH ₂ ) yi , - [NH- (CH ₂ ) y ₂ ] xi- and - [O- (CH 2) y ₃ ] x ₂ -, y ₁ , y ₂ and y ₃ independently representing an integer ranging from 1 to 6, and x _x and x ₂ representing, independently, an integer ranging from 1 to 4.

13. Use according to any one of claims 1 to 12 wherein the 1,3-dipolar compound is one of the compounds of formula (VIII) to (XIII):

(VIII) (IX)

The use according to any one of claims 1 to 13 wherein Q contains a -C = N (-> O) - motif, preferably includes the unit of formula (XIV) or (XV).

Y _r HC

(XIV)

Y 2

OR

and Y ₂ is an aliphatic group, preferably a saturated hydrocarbon group preferably containing 1 to 12 carbon atoms, or a group comprising an aromatic unit and preferably containing 6 to 20 carbon atoms, Y ₂ having a direct attachment to B.

15. Use according to claim 14 wherein the 1,3-dipolar compound is one of the 1,3-dipolar compounds of formula (XVI) to (XX):

(XIX) (XX) Y 1 being as defined in claim 14.

16. Use according to any one of claims 1 to 15 wherein the level of 1,3-dipolar compound ranges from 0.01 to 50 molar equivalents, preferably from 0.01 to 10 molar equivalents of group A per 100 moles of monomer units. constituting the diene elastomer.

17. Use according to any one of claims 1 to 16 wherein the reinforcing inorganic filler, preferably a silica, represents more than 50% by weight of the reinforcing filler.