WO2018015673A1

WO2018015673A1 - High strength rubber composition

Info

Publication number: WO2018015673A1
Application number: PCT/FR2017/051988
Authority: WO
Inventors: David DOISNEAU; Anne-Lise THUILLIEZ; Odile GAVARD-LONCHAY
Original assignee: Compagnie Generale Des Etablissements Michelin
Priority date: 2016-07-21
Filing date: 2017-07-20
Publication date: 2018-01-25

Abstract

The disclosed rubber composition comprises at least one resin that is based on: - an aromatic polyphenol containing at least one aromatic ring carrying at least two hydroxyl functions in the meta position relative to one another, the two ortho positions of at least one of the hydroxyl functions being unsubstituted; and - a compound obtained by reacting a reagent of formula A with a reagent of formula B and/or C; and mixtures of said compounds wherein: - Ar represents an optionally substituted aromatic ring; - each group R₁, R₂ independently represents a monovalent hydrocarbon group or a substituted monovalent hydrocarbon group.

Description

High stiffness rubber composition

The invention relates to rubber compositions, a method of making such compositions, uses of compounds in these compositions, a rubber composite and a tire.

It is known to use in certain tire parts, rubber compositions having a high rigidity at low tire deformations. Resistance to small deformations is one of the properties that must present a tire to respond to the stresses to which it is subjected.

[003] High rigidity can be obtained using a so-called concentrated vulcanization system, that is to say comprising, in particular, relatively high levels of sulfur and vulcanization accelerator.

[004] However, such a concentrated vulcanization system penalizes the raw aging of the composition. Thus, when the composition is in the form of a semi-finished product, for example a rubber band, the sulfur can migrate to the surface of the semi-finished product. This phenomenon, called touching, leads to a penalization of the raw tack of the semi-finished product during its prolonged storage, with consequent degradation of the adhesion between the semi-finished products during the manufacture of the tire.

Furthermore, the storage of the raw composition containing a concentrated vulcanization system is likely to cause a decrease in the delay phase of the composition during its vulcanization, that is to say the time before the start of vulcanization. As a result, the composition may begin to cook prematurely in some shaping tools and the vulcanization kinetics may be varied and the vulcanization yield may be degraded.

[006] Such a concentrated vulcanization system also penalizes cooked aging. Indeed, there is a degradation of the mechanical properties of the cooked composition, in particular at the limits, for example of elongation at break.

[007] High rigidity can otherwise be obtained by increasing the rate of reinforcing filler.

[008] However, in a known manner, increasing the rigidity of a rubber composition by increasing the loading rate can penalize the hysteresis properties and therefore the rolling resistance of the tires. However, we always try to lower the rolling resistance of tires to reduce fuel consumption and thus preserve the environment.

Finally, a high rigidity can be obtained by incorporating certain reinforcing resins as disclosed in WO 02/10269. [010] Conventionally, the increase in rigidity is obtained by incorporating reinforcing resins based on an acceptor / methylene donor system. The terms "methylene acceptor" and "methylene donor" are well known to those skilled in the art and widely used to design compounds capable of reacting together to generate by condensation a three-dimensional reinforcing resin which is superimposed and interpenetrated with the reinforcing filler / elastomer network on the one hand and with the elastomer / sulfur network on the other hand (if the crosslinking agent is sulfur). The methylene acceptor is associated with a curing agent, capable of crosslinking or hardening, also commonly called methylene donor. Examples of such acceptor and methylene donor are described in WO 02/10269.

[011] The methylene donors conventionally used in tire rubber compositions are hexamethylenetetramine (abbreviated to HMT), or hexamethoxymethylmelamine (abbreviated to HMMM or H3M), or hexaethoxymethylmelamine.

[012] Methylene acceptors conventionally used in tire rubber compositions are precondensed phenolic resins.

[013] However, the combination of phenolic resin conventionally used as a methylene acceptor with ΙΉΜΤ or ΙΉ3Μ as a methylene donor, produces formaldehyde during the vulcanization of the rubber composition. However, it is desirable to reduce or even eventually eliminate formaldehyde rubber compositions because of the environmental impact of these compounds and recent regulatory developments, including European regulations, on this type of compound.

The object of the invention is to provide a stiffened rubber composition by means of compounds with a low environmental impact.

[015] For this purpose, the subject of the invention is a rubber composition comprising at least one resin based on:

at least one aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted, and

at least one compound derived from a reagent of formula A:

(AT)

and a reagent of formula B and / or C: H

H ₂ N R-ι R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic nucleus, optionally substituted,

each Ri, R ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical.

[016] Unexpectedly, the Applicants discovered during their research that the compound of the composition according to the invention avoids the production of formaldehyde unlike conventional methylene donors. The Applicants have discovered during their research that a compound could, with an aromatic polyphenol, form an alternative resin to the reinforcing resins based on an acceptor / methylene donor system.

[017] In addition, the combination of the compound and the aromatic polyphenol according to the invention makes it possible to obtain rubber compositions having a stiffness at low deformation equivalent to, or even greater than, conventional rubber compositions which comprise HMT methylene donors or H3M and with respect to the rubber compositions lacking a reinforcing resin.

[018] In addition, the aromatic compounds and polyphenols according to the invention also make it possible to avoid early crosslinking of the resin. Indeed, a problem related to the use of certain reinforcing resins, in particular that based on the aromatic polyphenol and the aldehyde corresponding to the compound (the aldehyde of formula A), is their ability to crosslink early. Indeed, after the step of manufacturing the composition comprising the constituents of these reinforcing resins, the composition is shaped, for example by calendering, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile. However, because of their ability to rapidly crosslink, these reinforcing resins crosslink and stiffen the composition, which can hinder the shaping of the rubber composition. By virtue of the invention, the resin formed from the compound and the aromatic polyphenol forms less rapidly than from the corresponding aromatic aldehyde and polyphenol. This reaction rate can be determined by measuring the evolution of the rheometric torque as a function of time. This development describes the stiffening of the composition, in particular as a result of the crosslinking of the resin. Comparing the evolution of the rheometric pairs of a first composition comprising the aromatic polyphenol and the compound and a second composition comprising the aromatic polyphenol and the corresponding aldehyde, we see that the compound allows to delay the crosslinking of the resin relative to the direct reaction between the aromatic polyphenol and the corresponding aldehyde.

The inventors at the origin of the invention hypothesize that the compound is a precursor of the aldehyde (which would be the aldehyde of formula A) and that this compound makes it possible to avoid early crosslinking of the resin because of a reaction that would generate the aldehyde from the compound. Indeed, the reagents of formulas B and C act as temporary protective reagents allowing, according to the hypothesis of the inventors, the formation of each aldehyde function under predetermined reaction conditions and therefore the formation of the corresponding aldehyde (in other words regeneration of the aldehyde of formula A). The predetermined reaction conditions in which this formation is possible depend on several parameters such as the pressure, the temperature or the chemical species present in the reaction medium. These reaction conditions are a function of the reactants of formulas B and C and are easily determinable, even known to those skilled in the art. For example, such reaction conditions are heating the rubber composition to a temperature greater than or equal to 80 ° C, preferably 100 ° C and more preferably 120 ° C.

[020] Thus, by following this hypothesis, we will discuss in the following indifferently resin or phenol-aldehyde resin to identify the polyphenol-based resin and the compound resulting from the reaction of reagents A with B and / or C.

[021] The reagents of formulas B and C are such that the reaction between the aromatic polyphenol and the compound allows the crosslinking of the resin. Preferably, the reagents of formulas B and C are such that the reaction between the aromatic polyphenol and the compound makes it possible to crosslink the resin under the same reaction conditions, preferably the same reaction temperature conditions, as a phenol-aldehyde resin. based on the same aromatic polyphenol and the corresponding aldehyde (i.e. the aldehyde of formula A). In a conventional manner, the temperature is greater than or equal to 120 ° C., preferably greater than or equal to 140 ° C.

In addition, the aromatic compounds and polyphenols according to the invention also make it possible to maintain the rigidity of the composition at elevated temperatures, in particular for temperatures up to 150 ° C. In fact, the resin formed from the compound and the aromatic polyphenol has an improved temperature resistance compared to a resin formed from the aldehyde of formula A and the aromatic polyphenol. This temperature resistance can be determined by measuring the evolution of the rheometric torque as a function of time as described above. Polyphenol aromatic and the compound provide an extremely high torque value demonstrating excellent rigidity maintenance with the increase in temperature.

[023] As already explained above, the inventors at the origin of the invention hypothesize that the compound is a precursor of the aldehyde of formula A. As already explained above, this makes it possible to avoid immediate crosslinking of the resin due to a reaction that would generate, off-line, the aldehyde function from the compound. Indeed, the reagents of formulas B and C would act as temporary protective reagents allowing, according to the hypothesis of the inventors, the formation of each aldehyde function under predetermined reaction conditions (in other words the regeneration of the aldehyde of formula AT). The time taken to regenerate the aldehyde of formula A, even if it is very short, for example of the order of one minute, would allow a better dispersion of the compound and the aromatic polyphenol in the reaction mixture, which would make it possible to obtain a resin. having a more homogeneous crosslinking and therefore a better temperature resistance of the resin.

By the term "resin-based", it is of course understood to include a resin comprising the mixture and / or the product of the reaction between the different basic constituents used for the final condensation of this resin, preferably only the product of the reaction between the different basic constituents used for this resin, some of which may be intended to react or likely to react with one another or with their near chemical environment, at least in part, during the different phases of the process for manufacturing the composition, the composites or the tire, in particular during a cooking step. Thus, the basic constituents are the reactants intended to react together during the final condensation of the resin and are not reagents intended to react together to form these basic constituents.

[025] According to the invention, the basic constituents thus comprise at least one compound and at least one aromatic polyphenol. In one embodiment, the base components may comprise other additional additional components of the compound and the aromatic polyphenol. In another embodiment, the base components consist of at least one compound and at least one aromatic polyphenol.

[026] Preferably, in the embodiment where the basic constituents comprise other additional constituents, these other additional constituents are free of formaldehyde and / or devoid of a methylene donor selected from the group consisting of hexamethylenetetramine. (HMT), hexamethoxymethylmelamine (H3M), hexaethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, formaldehyde trioxane hexamethoxymethylmelamine polymers, rhexakis (methoxymethyl) melamine, N, N ', N " trimethyl / N, N ', N "- trimethylolmelamine, hexamethylolmelamine, N-methylolmelamine, Ν, Ν'-dimethylolmelamine, N, N ', N''- tris (methoxymethyl) melamine, N, N', N '' - tributyl-N, N These further additional components are free of formaldehyde and lack the methylene donors described in this paragraph.

[027] More preferentially, in the embodiment where the basic constituents comprise other additional constituents, these other additional constituents are free of formaldehyde and / or devoid of a methylene donor selected from the group consisting of hexamethylenetetramine, hexaethoxymethylmelamine, hexamethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, hexamethoxymethylmelamine trioxane and N-substituted oxymethylmelamines having the general formula:

wherein Q represents an alkyl group containing from 1 to 8 carbon atoms; F ₂ , F ₃ , F ₄ and F ₅ are chosen, independently of each other, from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms, by the group -CH20Q and their condensation products. More preferably, these other additional components are free of formaldehyde and lack the methylene donors described in this paragraph.

[028] Still more preferably, in the embodiment where the basic constituents comprise other additional constituents, these other additional constituents are free of formaldehyde and / or free of methylene donor. More preferably, these other additional components are free of formaldehyde and free of methylene donors.

[029] By lacking formaldehyde or without a methylene donor, it is meant that the total mass ratio of the formaldehyde or methylene donor (s) belonging to the groups described above by the total weight of the compound (s) according to the invention in the basic constituents is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

By "free from formaldehyde and devoid of methylene donor, it is meant that the total mass ratio of formaldehyde and methylene donor (s) belonging to the groups described above in total weight of the compound (s) according to the invention in the base constituents is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

According to the designation "aromatic polyphenol", the aromatic ring bearing at least two hydroxyl functional groups in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functional groups being substituted is a benzene ring.

By "meta position relative to each other", it will be understood that the hydroxyl functions are carried by carbons of the aromatic ring separated from each other by a single other carbon of the aromatic ring.

By "in the ortho position of a group" is meant the position occupied by the carbon of the aromatic ring immediately adjacent to the carbon of the aromatic ring bearing the group.

[034] The rubber composition therefore comprises at least one (that is to say one or more) crosslinked reinforcing resin, the reinforcing resin being constituted by the resin; this resin being based on at least one (that is to say one or more) compound and at least one (that is to say one or more) aromatic polyphenol, constituents which will be described in detail hereinafter -after.

[035] The subject of the invention is also a rubber composition comprising at least one resin based on:

at least one aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted , and

at least one compound selected from the group consisting of compounds of the following formulas:

(i) (he) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Z-i represents a monovalent radical chosen from the radicals of the following formulas:

Z ₂ represents a divalent radical of following formula:

in which each radical R 1, R ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical.

[036] Unlike the above, the compound is defined here by its structure and not by its method of production. The structures of the compound which acts as precursor of the aldehyde are those of the products obtained by reaction between the reactants of formulas A and B and / or C.

[037] The subject of the invention is also a rubber composition comprising:

at least one aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted, and at least one compound derived from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N Ri R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

each R 1, R ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical.

[038] The subject of the invention is also a rubber composition comprising:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Zi represents a monovalent radical chosen from the radicals of the following formulas:

Z ₂ represents a divalent radical of following formula

Another object of the invention is a method of manufacturing a rubber composition in the green state comprising a mixing step:

at least one compound derived from a reagent of formula A:

and a reagent of formula B and / or C

H ₂ N R-,

(B) (C) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

[040] Preferably, during the mixing step, at least one elastomer is also mixed with the composition.

[041] Another object of the invention is a method for manufacturing a raw rubber composition comprising a mixing step:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Z ₂ represents a divalent radical of following formula:

[042] Preferably, during the mixing step, at least one elastomer is also mixed with the composition.

[043] Another object of the invention is a method of manufacturing a rubber composition in the cooked state, comprising:

a step of manufacturing a rubber composition in the green state comprising a mixing step:

at least one compound resulting from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N R-, R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

each radical R1, R2 represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, - Then, a shaping step of the rubber composition in the green state,

then, a step of crosslinking, for example by vulcanization or baking, of the rubber composition during which a resin based on the aromatic polyphenol and the compound is crosslinked.

[044] Preferably, during the mixing step, at least one elastomer is also mixed with the composition.

Another object of the invention is a method of manufacturing a baked rubber composition, comprising:

at least one compound selected from the group consisting of the compounds of the following formulas:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Z ₂ represents a divalent radical of following formula:

in which each radical R 1, R ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, then a shaping step of the rubber composition in the green state,

[046] As previously explained, the inventors theorize that during the crosslinking step of the rubber composition, prior to crosslinking the resin,

a step of forming the aldehyde from the compound or precursor of the aldehyde by forming, on the aromatic ring Ar, at least one aldehyde function, and

a step of crosslinking a phenol-aldehyde resin from the aromatic polyphenol and the aldehyde.

[047] Yet another object of the invention is a rubber composition obtainable by a process as described above.

[048] The subject of the invention is also the use of a compound resulting from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N R- | R ₂ N Ri

(B) (C)

in which :

Ar represents an aromatic ring, optionally substituted,

each R 1, R ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, for the manufacture of a resin for reinforcing a rubber composition, the reinforcing resin being base of at least one aromatic polyphenol and at least one compound.

[049] The invention also relates to the use of a compound resulting from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N R- | R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

each R 1, R ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, in a rubber composition comprising a resin based on at least one aromatic polyphenol and at least one the compound for generating a delay phase during the crosslinking of the resin.

The invention also relates to a rubber composite reinforced with at least one reinforcement element embedded in a rubber composition as described above.

[051] Another object of the invention is a tire comprising a rubber composition as described above or a rubber composite as described hereinabove. above.

[052] By rubber composition is meant that the composition comprises at least one elastomer or a rubber (both terms being synonymous) and at least one other component. A rubber composition therefore comprises an elastomer or rubber matrix in which at least the other component is dispersed. A rubber composition is in a plastic state in the green (non-crosslinked) state and in a baked (crosslinked) elastic state but in no case in a liquid state. A rubber composition should not be confused with an elastomer latex which is a composition in a liquid state comprising a liquid solvent, usually water, and at least one elastomer or rubber dispersed in the liquid solvent so as to form an emulsion. Thus, the rubber composition is not an aqueous adhesive composition.

[053] In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are percentages by weight. The acronym "pce" means parts by weight per hundred parts of elastomer.

[054] On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., terminals a and b excluded ) while any range of values designated by the expression "from a to b" means the range of values from the terminal "a" to the terminal "b" that is to say including the strict limits " a "and" b ".

[055] In the context of the invention, the carbon products mentioned in the description may be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. [056] Reaction product between reagents A and B and / or C - Compound of the rubber composition

[057] According to the invention, the composition comprises one or more compound (s) of formula I and / or II obtained by the reaction between the reactants of formula A and B and / or C.

[058] The aldehyde generated from the compound is very advantageous. Indeed, the Applicants have discovered during their research that such an aldehyde having an aromatic ring bearing an aldehyde function makes it possible to avoid the production of formaldehyde, unlike conventional methylene donors. Indeed, the combination of phenolic resin conventionally used as a methylene acceptor with HMT or ΙΉ3Μ as a methylene donor in the state of the art, produces formaldehyde during the crosslinking of the rubber composition . However, it is desirable to reduce or even eventually eliminate the formaldehyde of the compositions of because of the environmental impact of these compounds and recent regulatory developments, including European regulations, on this type of compound.

[059] In one embodiment, Ar is a six-membered aromatic ring.

By "link" of a nucleus, one will hear a constituent atom of the skeleton of the nucleus. Thus, for example, a benzene ring comprises six members, each member being a carbon atom. Thus, the aromatic ring Ar comprises, as a link, carbon atoms and optionally one or more heteroatoms, in particular nitrogen, oxygen and sulfur atoms, optionally oxidized in the form of N-oxide or S-form. oxide.

[061] In a first variant of this six-membered aromatic ring embodiment, the remainder of the aromatic ring Ar is unsubstituted. In other words, the aromatic ring carries a single group consisting of the -CHO function. For example, in this first variant, when the six-membered aromatic ring is a benzene ring, the aldehyde generated from the compound is benzaldehyde.

[062] In a second variant of this six-membered aromatic ring embodiment, the aromatic ring Ar is di-substituted.

[063] Preferably, in certain embodiments of this second variant, the reagent A has, for example, the following formula Aa:

(Aa)

[064] Such a preferred reagent of formula Aa makes it possible to obtain the compounds of the following formulas:

(Nia) (IVa) (Va)

[065] The compound is therefore preferably selected from the group consisting of these compounds of formulas Nia, IVa, Va and mixtures thereof.

[066] Advantageously, the two substituents of the aromatic ring Ar are in the para position with respect to each other. By "position relative to each other" it will be understood that the functions referred to are the opposite of each other, that is to say in positions 1 and 4 of the aromatic nucleus with 6 members. Similarly, the "para position" with respect to a function is a position opposite to the function on the 6-membered aromatic ring carrying the function.

[067] Preferably, Ar is a benzene aromatic ring.

[068] In another embodiment, Ar is a five-membered aromatic ring.

[069] In a similar way to the definition given above, by "link" of a nucleus, we will hear a constituent atom of the skeleton of the nucleus. Thus, for example, a furan ring comprises five members, four members being each constituted by a carbon atom and the remaining member being an oxygen atom. Thus, the aromatic ring Ar comprises, as a link, carbon atoms and optionally one or more heteroatoms, in particular nitrogen, oxygen and sulfur atoms, optionally oxidized in the form of N-oxide or S- oxide.

[070] In a first variant of this embodiment of the five-membered aromatic ring, the remainder of the aromatic ring Ar is unsubstituted. In other words, the aromatic ring carries a single group consisting of the -CHO function.

[071] Preferably, in this first variant, the reagent of formula A has the following formula:

(Ab)

wherein X is N, S or O, preferably X is O.

[072] In this first variant, the aromatic ring Ar thus has the following formula:

wherein X is N, S or O, preferably X is O.

[073] In a variant of the reagent of formula A, the reagent of formula A or aldehyde used is then furfuraldehyde of formula Ab1:

[074] In another embodiment, X comprises N. Advantageously, X represents NH or NR ₄ with R ₄ representing a radical chosen from the group consisting of radicals monovalent alkylene, arylene arylalkylene, alkylarylene, cycloalkylene and alkenylene.

[075] In another embodiment, X comprises S. Advantageously, X represents S, SR ₅ , SR ₅ R ₅ ', S = O or O = S = O with R ₅ , R ₅ ' representing, independently, one on the other, a radical selected from the group consisting of monovalent alkylene, arylene arylalkylene, alkylarylene, cycloalkylene and alkenylene radicals.

[076] In a second variant of this five-membered aromatic ring embodiment, the remainder of the aromatic ring Ar is di-substituted.

[077] Preferably, in certain embodiments of this second variant, the reagent A has, for example, the following formula Aa ':

(Aa ')

[078] Such a preferred reagent of formula Aa 'makes it possible to obtain the compounds of the following formulas:

(IIIb) (IVb) (Vb)

[079] The compound is therefore preferably selected from the group consisting of these compounds of formulas IIIb, IVb, Vb and mixtures thereof.

[080] Preferably, in this second variant, the reagent of formula A has the following formula Ac:

(Ac)

wherein X is N, S or O, preferably X is O.

[081] In this second variant, the aromatic ring Ar therefore preferably has the following formula:

wherein X is N, S or O, preferably X is O. [082] Still more preferably, the reagent of formula A has the following formula Ad:

(Ad)

wherein X is N, S or O, preferably X is O.

[083] In this second variant, the two substituents of the aromatic ring Ar are thus even more preferably in position 2 and 5 with respect to each other.

[084] When X is O, the reagent of formula Ad is 2,5-furanedicarboxaldehyde.

[085] Thus, more preferably, the reagent of formula A is selected from the group consisting of 1,4-benzenedicarboxaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these reagents.

[086] Preferably, the composition is free of formaldehyde and / or free of a methylene donor selected from the group consisting of hexamethylenetetramine (HMT), hexamethoxymethylmelamine (H3M), hexaethoxymethylmelamine, lauryloxymethylpyridinium chloride , ethoxymethylpyridinium chloride, formaldehyde trioxane hexamethoxymethylmelamine polymers, rhexakis (methoxymethyl) melamine, N, N ', N "-trimethyl / -N, N', N" -trimethylolmelamine, hexamethylolmelamine, N-methylolmelamine, Ν, Ν'-dimethylolmelamine, Ν, Ν ', Ν "- tris (methoxymethyl) melamine, N, N', N" -tributyl-N, N ', N "-trimethylolmelamine More advantageously the composition is free of formaldehyde and devoid of the methylene donors described in this paragraph.

[087] More preferably, the composition is free of formaldehyde and / or free of a methylene donor selected from the group consisting of hexamethylenetetramine, hexaethoxymethylmelamine, hexamethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, trioxan hexamethoxymethylmelamine and N-substituted oxymethylmelamines having the general formula:

wherein Q represents an alkyl group containing from 1 to 8 carbon atoms; F ₂ , F ₃ , F ₄ and F ₅ are chosen, independently of each other, from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms, by the group -CH20Q and their condensation products. More preferably, the composition is free of formaldehyde and free of the methylene donors described in this paragraph.

[088] Still more preferably, the composition is free of formaldehyde and / or free of methylene donor. More preferably, the composition is free of formaldehyde and free of methylene donors.

[089] By depriving formaldehyde or without a methylene donor, it is meant that the total mass ratio of formaldehyde or methylene donor (s) belonging to the groups described above in total weight of the compound (s) according to the invention in the composition is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

By "free from formaldehyde and devoid of methylene donor" is meant that the total mass ratio of formaldehyde and methylene donor (s) belonging to the groups described above in total weight of the compound (s) according to the invention in the composition is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

[091] In one embodiment, the radical R 1 represents a monovalent radical chosen from the group consisting of alkyl, aryl, AL-NH ₂ radicals with AL representing a monovalent alkyl radical, AR-NH ₂ with AR representing a monovalent radical. aryl, AL-NR ₂ H with AL representing a monovalent alkyl radical and AR-NR ₂ H with AR representing a monovalent aryl radical. In this embodiment, reagent B can therefore be a primary amine (alklyl and aryl radicals), a primary diamine (AL-NH ₂ radicals, AR-NH ₂ ) or a diamine comprising a primary amine function and a secondary amine function. . In this embodiment, the reagent C can therefore be a secondary amine (alklyl radicals and aryl), a secondary diamine (radicals AL-NR ₂ H and AR-NR ₂ H) or a diamine comprising a primary amine function and a secondary amine function.

[092] Preferably, the radical R represents a monovalent radical selected from the group consisting of the radicals G-NH ₂ with G is a monovalent alkyl radical, AR-NH ₂ with AR is a monovalent aryl radical, U-NR ₂ H with AL representing a monovalent alkyl radical and AR-NR ₂ H with AR representing a monovalent aryl radical. The use of a primary or secondary diamine makes it possible, during the regeneration of the aldehyde from the compound, to generate a diamine in the rubber composition which can be used as a reactive molecule with respect to other molecules present in the composition, for example vis-à-vis the molecules involved in the vulcanization reaction to accelerate the start of vulcanization.

[093] More preferentially, the monovalent alkyl radical AL is a linear alkyl radical comprising a number of carbon atoms ranging from 1 to 15, preferably from 2 to 12 and more preferably from 2 to 8.

[094] In another embodiment, the radical Ri has the following formula:

in which R ₃ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical.

[095] In a first variant, R ₃ represents a monovalent radical chosen from the group consisting of the alkylene, arylene, arylalkylene, alkylarylene, cycloalkylene and alkenylene radicals, preferably from the group consisting of the alkylene and arylene radicals. In this variant, the reagent B or C may be a primary amide (reagent B) or secondary amide (reagent C).

[096] In a second variant, the radical R 1 is chosen from the group consisting of the radicals of the following formulas:

wherein R ₃ 'represents a divalent radical selected from the group consisting of alkylene, arylene, arylalkylene, alkylarylene, cycloalkylene, alkenylene radicals.

[097] More preferentially, the divalent alkylene radical R ₃ 'is a linear alkylene radical comprising a number of carbon atoms ranging from 1 to 15, preferably from 2 to 12, and more preferably from 2 to 8.

In this variant, the reagent B or C may be a primary di-amide (reagent B) or secondary (reagent C) or a diamide comprising a primary amide and a secondary amide.

[099] In yet another embodiment, the radical R 1 has the following formula:

in which R ₃ is NH ₂ .

In this other embodiment, the reagent B is urea.

[0101] Advantageously, the radical R ₂ is a monovalent radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl and alkenyl.

Advantageously, each radical R 1, R ₂ is devoid of reactive function with respect to an aromatic polyphenol. By reactive function is meant here a function that would react under reaction conditions necessary for the regeneration of the aldehyde of formula A and in the reaction conditions necessary for the crosslinking of the resin. Very preferably, each radical R 1, R ₂ is, for example, devoid of aldehyde and hydroxymethyl function.

[0103] Aromatic polyphenol of the rubber composition

According to the invention, the aromatic polyphenol may be a single molecule comprising one or more aromatic nuclei, at least one of these aromatic nuclei, or even each aromatic nucleus carrying at least two hydroxyl functional groups in the meta position, one of which relative to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted. Such a simple molecule does not include a repetitive pattern.

According to the invention, the aromatic polyphenol may be, in another embodiment, a pre-condensed resin based on:

at least one aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functions being substituted; and

at least one compound capable of reacting with the polyphenol comprising at least one aldehyde function, for example an aromatic aldehyde bearing at least one aldehyde function, comprising at least one aromatic nucleus but alternatively a non-aromatic aldehyde, for example formaldehyde and / or at least one compound capable of reacting with said aromatic polyphenol comprising at least two hydroxymethyl functional groups carried by an aromatic nucleus.

Such a pre-condensed resin based on aromatic polyphenol is in accordance with the invention and comprises, in contrast to the simple molecule described above, a repeating unit. In this case, the repeating unit comprises at least one aromatic ring bearing at least two hydroxyl functional groups in the meta position relative to one another.

In another embodiment, the aromatic polyphenol is a mixture of an aromatic polyphenol forming a single molecule and a pre-condensed resin based on aromatic polyphenol.

In the particular embodiments which follow, the aromatic ring (s) of the aromatic polyphenol is described. For the sake of clarity, the term "aromatic polyphenol" is described in its simple molecule form. This aromatic polyphenol may then be condensed and will partly define the repeating unit. The characteristics of the pre-condensed resin are described in more detail below.

In a preferred embodiment, the aromatic ring of the aromatic polyphenol carries three hydroxyl functional groups in the meta position relative to one another.

[0110] Preferably, the two ortho positions of each hydroxyl function of the aromatic polyphenol are unsubstituted. By this is meant that the two carbon atoms located on both sides (in the ortho position) of the carbon atom bearing the -O-H group carry a single hydrogen atom.

Even more preferably, the remainder of the aromatic ring of the aromatic polyphenol is unsubstituted. By this is meant that other carbon atoms of the rest of the aromatic ring (those other than the carbon atoms bearing -O-H groups) carry a single hydrogen atom.

In one embodiment, the aromatic polyphenol comprises a plurality of aromatic nuclei, at least two of which are each carrying at least two hydroxyl functional groups in the meta position with respect to each other, the two positions ortho of at least one of the hydroxyl functions of at least one aromatic ring being unsubstituted.

In a preferred embodiment, at least one of the aromatic rings of the aromatic polyphenol carries three hydroxyl functions in the meta position with respect to one another.

Preferably, the two ortho positions of each hydroxyl function of at least one aromatic ring are unsubstituted.

Even more preferentially, the two ortho positions of each hydroxyl function of each aromatic ring are unsubstituted. Even more preferably, the remainder of each of the aromatic rings is unsubstituted. By this is meant that the other carbon atoms of the remainder of each aromatic ring (those other than the carbon atoms carrying the hydroxyl functions or bearing the group linking the aromatic rings between them) carry a single hydrogen atom.

Advantageously, each aromatic ring of the aromatic polyphenol is a benzene ring.

As an example of an aromatic polyphenol comprising a single aromatic nucleus, mention may be made in particular of resorcinol and phloroglucinol, of formulas 10 and 11, respectively:

(10) (11)

As examples, in the case where the aromatic polyphenol comprises several aromatic rings, at least two of these aromatic nuclei, identical or different, are chosen from those of general formulas:

(12-b) (12-c) (12-d) in which the symbols Ti, T ₂ , which are identical or different if they are several on the same aromatic ring, represent an atom (for example carbon, sulfur or oxygen) or an at least divalent linking group, which connects at least these two aromatic rings to the rest of the aromatic polyphenol.

Another example of an aromatic polyphenol is 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, having the following formula:

Another example of an aromatic polyphenol is 2,2 ', 4,4'-tetrahydroxydiphenyl benzophenone, of the following formula:

(14)

It is noted that each compound 13 and 14 is an aromatic polyphenol comprising two aromatic rings (of formulas 12-c) each of which carries at least two (in this case two) -OH groups in the meta-l position. one with respect to the other.

Note that in the case of an aromatic polyphenol having at least one aromatic ring according to formula 12-b, the two ortho positions of each -O-H group of at least one aromatic ring are unsubstituted. In the case of an aromatic polyphenol having a plurality of aromatic rings according to formula 12-b, the two ortho positions of each -O-H group of each aromatic ring are unsubstituted.

Advantageously, the aromatic polyphenol is chosen from the group consisting of resorcinol, phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, 2,2', 4,4'-tetrahydroxybenzophenone, and mixtures of these compounds, preferably the aromatic polyphenol is phloroglucinol.

According to one embodiment of the invention, the aromatic polyphenol is chosen from the group consisting of resorcinol 10, phloroglucinol 11, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide 13, 2,2 4,4'-Tetrahydroxybenzophenone 14 and mixtures of these aromatic polyphenols. In a particularly advantageous embodiment, the aromatic polyphenol is phloroglucinol 11.

In one embodiment, the aromatic polyphenol comprises a precondensed resin based on aromatic polyphenol as described in any one of these embodiments.

This pre-condensed resin is advantageously based on: at least one aromatic polyphenol as defined above, and preferentially chosen from the group consisting of resorcinol, phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, 2,2', 4,4 tetrahydroxybenzophenone, and mixtures thereof; and

- At least one compound capable of reacting with the polyphenol comprising at least one aldehyde function and / or at least one compound capable of reacting with the polyphenol comprising at least two hydroxymethyl functions carried by an aromatic ring.

The compound capable of reacting with the polyphenol comprising at least one aldehyde function and / or the compound capable of reacting with the polyphenol comprising at least two hydroxymethyl functions carried by an aromatic ring may be a compound of formula A as defined above a compound of formula Ar- (CHO) ₂ , wherein Ar is as defined above for the compound of formula A, or any other aldehyde. Advantageously, said compound capable of reacting with the polyphenol comprising at least one aldehyde function and / or said compound capable of reacting with the polyphenol comprising at least two hydroxymethyl functional groups carried by an aromatic nucleus is chosen from the group consisting of an aromatic compound comprising a an aromatic ring carrying at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function, formaldehyde, benzaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde,

1,2-benzenedicarboxaldehyde and mixtures thereof. Very advantageously, when the compound is an aromatic compound comprising an aromatic ring bearing at least two functions, one of these functions being a hydroxymethyl function, the other being an aldehyde function or a hydroxymethyl function, this compound is chosen from the group consisting of 5- (hydroxymethyl) -furfural, 2,5-di (hydroxymethyl) furan and mixtures of these compounds.

Thus, in the pre-condensed resin based on aromatic polyphenol, the repeating unit meets the characteristics of the aromatic polyphenol defined above with the exception that at least one of the carbon atoms of the aromatic ring, which was unsubstituted, is connected to another pattern.

Whatever the compound other than the aromatic polyphenol at the base of the pre-condensed resin, this pre-condensed resin is free of free formaldehyde. Indeed, even in the case where the pre-condensed resin is based on an aromatic polyphenol as described above and formaldehyde, formaldehyde having already reacted with the aromatic polyphenol, the pre-condensed resin is free of free formaldehyde capable of being able to react with the aromatic polyphenol according to the invention in a subsequent step.

The aromatic polyphenol may also comprise a mixture of an aromatic polyphenol free molecule and a pre-condensed aromatic polyphenol resin, as described above. In particular, the aromatic polyphenol may also comprise a mixture of phloroglucinol and a pre-condensed phloroglucinol resin.

[0132] Rubber compositions according to the invention

Depending on the use of the composition, a quantity of compound ranging from 0.1 to 25 phr will be used. Likewise, a quantity of aromatic polyphenol derivative ranging from 0.1 to 25 phr will be used.

According to the use that is made of the composition, the rubber composition has, in the fired state, a secant modulus at 10% elongation MA10 measured according to ASTM D 412 of 1998 (specimen C ) greater than or equal to 10 MPa, preferably 20 MPa, preferably 30 MPa, more preferably 40 MPa and even more preferably 60 MPa.

[0135] Preferably, the rubber composition comprises a diene elastomer.

By elastomer or rubber (both terms being synonymous) of the "diene" type, is generally meant an elastomer derived at least in part (ie a homopolymer or a copolymer) from monomers dienes (monomers carrying two double bonds carbon-carbon, conjugated or not).

In a particularly preferred manner, the diene elastomer of the rubber composition is chosen from the group consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, copolymers of isoprene and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers butadiene-styrene (SBIR) and mixtures of such copolymers.

The rubber compositions may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer or elastomers that may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers. for example thermoplastic polymers.

[0139] Preferably, the rubber composition comprises a reinforcing filler. When a reinforcing filler is used, it is possible to use any type of 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 filler reinforcing inorganic such as silica, or a blend of these two types of filler, including a blend of carbon black and silica.

As carbon blacks are suitable all carbon blacks conventionally used in tires (so-called pneumatic grade black). For example, mention will be made more particularly of reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades).

In the case of using carbon blacks with an isoprene elastomer, the carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch (see for example applications WO 97/36724). or WO 99/16600).

As examples of organic fillers other than carbon blacks, mention may be made of the organic functionalized polyvinylaromatic fillers as described in applications WO-A-2006/069792 and WO-A-2006/069793.

By "reinforcing inorganic filler" is meant in the present application, by definition, any inorganic or mineral filler (whatever its color and origin (natural or synthetic), also called "white" charge, charge "clear" or "non-black filler" as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition for manufacturing In other words, it can replace, in its reinforcing function, a conventional carbon black of pneumatic grade, such a charge is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) at its area.

The physical state in which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form. Of course, the term "reinforcing inorganic filler" also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.

As reinforcing inorganic fillers are particularly suitable inorganic fillers of the siliceous type, in particular silica (SiO ₂ ), or of the aluminous type, in particular alumina (Al ₂ O ₃ ). The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface and a CTAB specific surface area both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g. As highly dispersible precipitated silicas (called "HDS"), mention may be made, for example, of the "Ultrasil" 7000 and "Ultrasil" silicones 7005 from the Evonik company, the "Zeosil" 1165MP, 1135MP and 1115MP silicas from the Rhodia company, the "Hi-Sil" silica EZ150G from the PPG company, the "Zeopol" 8715, 8745 and 8755 silicas from the Huber Company, the high surface area silicas as described in the application WO 03/16837.

Finally, a person skilled in the art will understand that, as an equivalent load of the reinforcing inorganic filler described in this paragraph, a reinforcing filler of another nature, in particular organic, could be used provided that this reinforcing filler would be covered with an inorganic layer such as silica, or would comprise on its surface functional sites, especially hydroxyl, requiring the use of a coupling agent to establish the bond between the filler and the elastomer.

Preferably, the content of total reinforcing filler (carbon black and / or reinforcing inorganic filler such as silica) is in a range from 5 to 120 phr, more preferably from 5 to 100 phr and even more preferably from 5 to 100 phr. at 90 pce.

The carbon black may advantageously be the only reinforcing filler or the majority reinforcing filler. Of course, it is possible to use a single carbon black or a blend of several carbon blacks of different ASTM grades. The carbon black may also be used in blending with other reinforcing fillers and in particular reinforcing inorganic fillers as described above, and in particular silica.

When an inorganic filler (for example silica) is used in the rubber composition, alone or in combination with carbon black, its content is within a range from 0 to 70 phr, preferably from 0 to 70 phr. 50 phr, in particular also from 5 to 70 phr, and even more preferably this proportion varies from 5 to 50 phr, particularly from 5 to 40 phr.

[0151] Preferably, the rubber composition comprises various additives.

The rubber compositions may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tires, for example plasticizers or extension oils, which are of aromatic nature. or non-aromatic, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents or even adhesion promoters.

[0153] Preferably, the rubber composition comprises a crosslinking system, more preferably a vulcanization system.

The vulcanization system comprises a sulfur donor agent, for example sulfur. [0155] Preferably, the vulcanization system comprises vulcanization activators such as zinc oxide and stearic acid.

[0156] Preferably, the vulcanization system comprises a vulcanization accelerator and / or a vulcanization retarder.

Sulfur or sulfur donor agent is used at a preferred level within a range of 0.5 to 10 phr, more preferably in a range of 0.5 to 8.0 phr. All accelerators, retarders and vulcanization activators are used at a preferential rate within a range of 0.5 to 15 phr. The vulcanization activator (s) is or are used at a preferential rate within a range of 0.5 and 12 phr.

The crosslinking system itself is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator. To this vulcanization system are added, various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (in particular diphenylguanidine), etc.

It is possible to use as accelerator (primary or secondary) any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, especially thiazole accelerators and their derivatives, thiuram type accelerators, and zinc dithiocarbamate type. These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), Ν, Ν-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazylsulfenamide (abbreviated "TBBS"), N-tert-butyl-2-benzothiazylsulfenimide (abbreviated "TBSI"), zinc dibenzyldithiocarbamate (in abbreviated "ZBEC") and mixtures of these compounds. Preferably, a primary accelerator of the sulfenamide type is used.

In one embodiment, the rubber composition is in the fired state, that is to say vulcanized. In other embodiments, the composition is in a green, i.e., unvulcanized state with the crosslinked resin subsequently added to the unvulcanized composition.

In some embodiments, the composition comprises a residue obtained from the Z-ι and / or Z ₂ radical. Prior to curing the resin, and as assumed by the inventors at the origin of the invention, after formation of the aldehyde function, each Z-ι radical and / or Z ₂ can achieve a residue generated in- if you. Some residues remain definitively in the composition and, if necessary, can be used for some of their properties. In other embodiments, the generated residue remains only temporarily in the composition either because it comes out spontaneously under the conditions of manufacture of the composition, for example in the form of gas, especially in the case where the residue is volatile, or because it implements an optional step of extracting this residue in the method of manufacturing the composition.

In one embodiment, the resin having not yet crosslinked, the rubber composition comprises:

at least one aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functional groups in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted, and

(AT)

and a reagent of formula B and / or C:

H

H ₂ N R- | R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic nucleus, optionally substituted,

In this embodiment, the compound resulting from the reaction between the reagents A and B and / or C is chosen from the following formulas:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted, Z represents a monovalent radical chosen from the radicals of the following formulas:

Z ₂ represents a divalent radical of following formula

[0165] Preferably, in this embodiment, the composition is in the green state, that is to say unvulcanized.

Preferably, the rubber composition may be used in the tire in the form of a layer. By layer is meant any three-dimensional element, of any shape and thickness, in particular sheet, strip or other element of any cross section, for example rectangular or triangular.

Of course, all the characteristics relating to the aromatic polyphenol and to the compound of the composition comprising the resin also apply to the composition comprising the aromatic polyphenol and the non-crosslinked compound in the resin state. [0168] Rubber composite according to the invention

The rubber composite is reinforced with at least one reinforcement element embedded in the rubber composition according to the invention.

This rubber composite may be prepared according to a process comprising at least the following steps:

in a first step, combining at least one reinforcing element with a rubber composition (or elastomer, both terms being synonymous) to form a reinforced rubber composite of the reinforcing element;

then, during a second step, crosslinking by baking, for example by vulcanization, preferably under pressure, the composite thus formed.

Among the reinforcing elements, mention may be made of textile, metal or hybrid textile-metal reinforcing elements.

By textile means, in a manner well known to those skilled in the art, any material other than metallic material, whether natural as synthetic, capable of being transformed into yarn, fiber by any process of transformation appropriate. For example, without the following examples being limiting, there may be mentioned a polymer spinning process such as, for example, melt spinning, solution spinning or gel spinning.

This textile material may consist of a yarn or fiber or also of a fabric made from yarn or fibers, for example a woven fabric with warp yarns and weft yarns, or a fabric crossed with crossed threads.

Preferably, this textile material of the invention is chosen from the group consisting of monofilaments (or single son), multifilament fibers, assemblies of such son or fibers, and mixtures of such materials. It is more particularly a monofilament, a multifilament fiber or a twist.

By wire or fiber is generally meant any elongate element of great length relative to its cross section, whatever the shape of the latter, for example circular, oblong, rectangular or square, or even flat, this wire can be rectilinear as non-rectilinear, for example twisted or corrugated. The largest dimension of its cross section is preferably less than 5 mm, more preferably less than 3 mm.

This wire or this fiber may take any known form, it may be for example an elementary monofilament of large diameter (for example and preferably equal to or greater than 50 μηη), a multifilament fiber (constituted of a plurality of elementary filaments of small diameter, typically less than 30 μηη), of a twisted or cabled textile formed of several textile fibers or monofilaments twisted or cabled together, or of an assembly, a group, a row of yarns or fibers such as for example a band or strip comprising several of these monofilaments, fibers, twisted or cabled grouped together, for example aligned in a main direction, rectilinear or not.

The textile materials may be organic or polymeric material, such as inorganic material.

As examples of inorganic materials, mention will be made of glass and carbon.

The invention is preferably implemented with materials of polymeric material, thermoplastic type as non-thermoplastic.

Examples of polymeric materials of the non-thermoplastic type include aramid (aromatic polyamide) and cellulose, natural as artificial, such as cotton, rayon, linen, hemp.

As examples of polymeric materials of the thermoplastic type, mention will preferably be made of aliphatic polyamides and polyesters. Among the aliphatic polyamides that may be mentioned in particular are polyamides 4-6, 6, 6-6, 11 or 12. Among the polyesters that may be mentioned for example PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene) terephthalate), PBN (polybutylene naphthalate), PPT (polypropylene terephthalate), PPN (polypropylene naphthalate).

By "metallic" is meant by definition one or more wire elements constituted mainly (that is to say for more than 50% of its mass) or integrally (for 100% of its mass) of a metallic material. Preferably, the metallic material is steel, more preferably carbonaceous perlitic (or ferrito-pearlitic) steel advantageously comprising between 0.4% and 1.2% by weight of carbon.

The metal reinforcing element can be a monofilament, a cable comprising several metal monofilaments or a multi-strand cable comprising several cables then called strands.

In the preferred case where the reinforcing element comprises several metal monofilaments or several strands, the metal monofilaments or the strands are assembled by twisting or wiring. It is recalled that there are two possible techniques of assembly:

either by twisting: the metal monofilaments or the strands undergo both a collective twist and an individual twist around their own axis, which generates a couple of untwist on each of the monofilaments or strands;

either by cabling: the metal monofilaments or the strands undergo only a collective torsion and do not undergo individual torsion around their own axis.

[0185] Optionally, the reinforcing element comprises several monofilaments and is of the type gummed in situ, that is to say that the reinforcing element is gummed from the inside, during its manufacture even by a rubber filling. Such wired elements metal are known to those skilled in the art. The composition of the filling rubber may or may not be identical to the rubber composition in which the reinforcing element is embedded. Γ01861 Pneumatic tire according to the invention

Such tires are for example those intended to equip tourism-type motor vehicles, SUV ("Sport Utility Vehicles"), two wheels (including bicycles, motorcycles), aircraft, such as industrial vehicles chosen from vans, " Heavy goods vehicles "- that is to say metro, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles -, other transport vehicles or Handling.

By way of example, the appended FIG. 1 shows very schematically (without respecting a specific scale) a radial section of a tire according to the invention for a heavy vehicle type vehicle.

This tire 1 comprises a top 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a rod 5. The top 2 is surmounted by a strip of bearing not shown in this schematic figure. A carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1 which is shown here mounted on its rim 9. The carcass reinforcement 7 is in known manner constituted of at least one sheet reinforced by so-called "radial" cables, for example metallic, that is to say that these cables are arranged substantially parallel to each other and extend from a bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located midway between the two beads 4 and passes through the middle of the crown frame 6).

This tire 1 of the invention has for example the characteristic that at least one crown reinforcement 6 and / or its carcass reinforcement 7 comprises a rubber composition or a composite according to the invention. Of course, the invention relates to the objects previously described, namely the rubber composite and the tire, both in the green state (before firing or vulcanization) and in the fired state (after firing or vulcanization).

[0191] Process for producing the compound according to the invention

The reaction between the reagent of formula A and the reagent of formula B and / or C is carried out in a polar solvent. Preferably, the solvent is selected from the group consisting of tetrahydrofuran, ether and water and more preferably the solvent is water. Water is particularly advantageous because, on the one hand, it is non-reactive with respect to reagents A, B and C and makes it possible to solubilize these reagents and, on the other hand, makes it possible to easily extract the compound according to the invention which there is no or very little soluble. In addition, by carrying out the reaction in water in which the compound is not or very slightly soluble, it precipitates and can not be hydrolyzed to give the reactants A, B and / or C starting.

In one embodiment, the reaction is carried out with a molar excess of reagent B and / or C relative to reagent A. Molar excess means that once the reaction is carried out, it remains at least 10% the initial molar amount of reagent B and / or C in the reaction medium.

In one embodiment in which the compound precipitates in the reaction medium, in order to wash the compound, the compound is washed with water, preferably with water having a temperature greater than room temperature. A sufficiently high temperature will be used to promote the solubilization of any excess of reagent B and / or C and other impurities, for example at a temperature above 50 ° C.

[0195] Process for manufacturing the composition according to the invention

The manufacturing method described above and hereinafter makes it possible to manufacture the composition according to the invention.

The rubber composition may be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art:

a first phase of work or thermomechanical mixing (so-called "nonproductive" phase) at high temperature, up to a maximum temperature of between 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C.,

followed by a second phase of mechanical work (so-called "productive" phase) to a lower temperature, typically below 110 ° C, for example between 40 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system.

In one embodiment, the method comprises the following steps:

- Incorporating into an elastomer, during a first step, a reinforcing filler, thermomechanically kneading the whole, until a maximum temperature between 1 10 ° C and 190 ° C;

- cool the assembly to a temperature below 1 10 ° C;

- Then incorporate, in a second step, a crosslinking system, the aromatic polyphenol and the compound;

- mix at a temperature below 1 10 ° C. For example, the non-productive phase is conducted in a single thermomechanical step during which is introduced, in a suitable mixer such as a conventional internal mixer, in a first step all the basic constituents necessary (diene elastomer, reinforcing filler, etc.), then in a second step, for example after one to two minutes of mixing, the other additives, any optional charge recovery or implementation agents, with the exception of of the crosslinking system, the aromatic polyphenol and the compound. The total mixing time in this non-productive phase is preferably between 1 and 15 minutes.

After cooling the mixture thus obtained, it is then incorporated in an external mixer such as a roll mill, maintained at low temperature (for example between 40 ° C. and 100 ° C.), the crosslinking system, the compound and aromatic polyphenol. The whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.

The composition thus obtained in the green state can then be shaped, for example calendered, for example in the form of a sheet, a plate especially for a characterization in the laboratory, or extruded, for example to form a rubber profile used for the manufacture of a tire.

Then, after a possible step of assembling together several compositions shaped webs or strips in the form of a composite or an uncured tire blank, a crosslinking step is carried out, for example by a crosslinking step of the composition, the composite or the blank during which the resin based on the aromatic polyphenol and the compound is crosslinked. The crosslinking step, here of vulcanization, is carried out at a temperature greater than or equal to 120 ° C., preferably greater than or equal to 140 ° C. The composition is obtained in the cooked state.

[0203] In another embodiment, the method comprises the following steps:

- Incorporating into an elastomer, during a first step, a reinforcing filler, the aromatic polyphenol and the compound, thermomechanically kneading the whole, until a maximum temperature of between 110 ° C and 190 ° C;

- cool all at a temperature below 110 ° C;

- Then incorporate, in a second step, a crosslinking system;

- mix at a temperature below 110 ° C.

[0204] Use of the compounds

In a particular embodiment, the use of the compound resulting from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N Ri R ₂ N Ri

(B) (C)

in which :

Ar represents an aromatic ring, optionally substituted,

the radical R 1 represents a monovalent radical chosen from the group consisting of alkyl, aryl, AL-NH ₂ radicals with AL representing a monovalent alkyl radical, AR-NH ₂ with AR representing a monovalent aryl radical, AL-NR ₂ H with AL representing a monovalent alkyl radical and AR-NR ₂ H with AR representing a monovalent aryl radical,

the radical R ₂ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical;

allows the manufacture of a reinforcing resin of a rubber composition, the reinforcing resin being based on at least one aromatic polyphenol and at least the compound.

In another embodiment independent of or in combination with the preceding embodiment, the use of the compound resulting from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N Ri R ₂ N Ri

(B) (C)

in which :

Ar represents an aromatic ring, optionally substituted,

the radical R 1 represents a monovalent radical chosen from the group consisting of alkyl, aryl, AL-NH ₂ radicals with AL representing a monovalent alkyl radical, AR-NH ₂ with AR representing a monovalent aryl radical, AL-NR ₂ H with AL representing a monovalent alkyl radical and AR-NR ₂ H with AR representing a monovalent aryl radical, the radical R ₂ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical;

allows, in a rubber composition comprising a resin based on at least one aromatic polyphenol and at least the compound, to generate a delay phase during the crosslinking of the resin.

In yet another embodiment, the use of the compound resulting from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N Ri R ₂ N Ri

(B) (C)

in which :

Ar represents an aromatic ring, optionally substituted,

the radical Ri has the following formula:

in which R ₃ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical or NH ₂ ,

the radical R ₂ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical

allows the manufacture of a reinforcing resin of a rubber composition, the reinforcing resin being based on at least one aromatic polyphenol and at least one compound.

(AT)

and a reagent of formula B and / or C: H ₂ N Ri R ₂ N Ri

(B) (C)

in which :

Ar represents an aromatic ring, optionally substituted,

the radical Ri has the following formula:

The invention as well as its advantages will be readily understood in the light of the following exemplary embodiments.

[0210] Examples of embodiment of the invention and comparative tests

[0211] These tests demonstrate that:

the rigidity of the rubber composition is greatly increased with respect to a rubber composition devoid of reinforcing resin;

the rigidity of the rubber composition according to the invention is maintained at high temperatures, in particular for temperatures up to 150 ° C.

there is a delay phase during the crosslinking of the resin of the composition according to the invention making it possible to avoid early crosslinking of the resin with respect to a phenol-aldehyde resin crosslinked directly from the aromatic polyphenol and the aldehyde corresponding (the aldehyde of formula A);

- The resin of the composition using the compound is free of formaldehyde and does not generate during its formation.

For this, several rubber compositions, hereinafter noted T0, T1 and 11 to 13 were prepared as indicated above and are summarized in Table 1 attached below.

All compositions T0, T1 and 11 to 13 have a common part in their formulations (expressed in phr, parts by weight per hundred parts of elastomer): 100 phr of natural rubber, 75 phr of N326 carbon black, 1.5 phr of N-1,3-dimethylbutyl-N-phenyl-para phenylenediamine, 1.5 phr of stearic acid, 5 phr of ZnO, 1 phr of N-tertiarybutyl-2-benzothiazole sulfonamide and 7 phr of insoluble sulfur 20H.

The composition T0 does not include any reinforcing resin added to this common part.

In addition to the common part, the composition T1 comprises a phenol-aldehyde resin based on phloroglucinol and 1,4-benzene-dicarboxaldehyde. The composition T1 comprises 14 phr of phloroglucinol and 14 phr of 1,4-benzenedicarboxaldehyde.

In addition to the common part, each composition 11 to 13 comprises an aromatic polyphenol and a compound forming a precursor of an aromatic aldehyde, indicated in Table 1 in molar proportions 1 (aromatic polyphenol) / 1 (compound) for compositions 11 and 12 and 2 (aromatic polyphenol) / 1 (compound) for composition 13, and with in each composition 11 to 13, 14 phr aromatic polyphenol.

The compositions T0 and T1 are not in accordance with the invention contrary to the compositions 11 to 13 which are in accordance with the invention.

In the raw state, each rubber composition 11 to 13 according to the invention comprises:

at least one compound derived from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N R- | R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic nucleus, optionally substituted,

In the fired state, each rubber composition 11 to 13 according to the invention comprises a resin based on: at least one aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted, and

(AT)

and a reagent of formula B and / or C:

H

H ₂ N Ri R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

As explained above, the compound resulting from the reaction between the reactants of formulas A and B and / or C is chosen from the group consisting of the compounds of the following formulas:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Z 1 represents a monovalent radical chosen from the radicals of the following formulas:

Z ₂ represents a divalent radical of following formula

[0221] Aromatic polyphenol of compositions 11 to 13

The aromatic polyphenol of each rubber composition 11 to 13 is selected from the group consisting of resorcinol, phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, 2,2', 4,4 -Tetrahydroxybenzophenone, and mixtures of these compounds, preferably the aromatic polyphenol is phloroglucinol. Each aromatic polyphenol of each composition 11 to 13 according to the invention comprises a single aromatic ring, here benzene, bearing three, and only three, -OH groups in the meta position relative to each other. The remainder of the aromatic ring of the aromatic polyphenol is unsubstituted. In particular, the two ortho positions of each -OH group are unsubstituted. The aromatic polyphenol of compositions 11 to 13 is phloroglucinol. Compound C1 precursor of the aldehyde of the composition 11

The compound C1 of the compound has a general formula Nia:

and is such that Ar is a di-substituted six-membered aromatic ring, in this case a benzene, and wherein 7.sub.1 is selected from the radicals of the following formulas:

in which R1 has the following formula:

in which R ₃ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical. In this case, R ₃ represents a monovalent radical chosen from the group consisting of the alkylene, arylene, arylalkylene, alkylarylene, cycloalkylene and alkenylene radicals, preferably from the group consisting of the alkylene and arylene radicals. Here, R ₃ represents the benzyl radical.

The compound C1 of the composition 11 is therefore a mixture of two compounds C1a and C1b having the following formulas:

The compound C1 of the composition 11 is therefore derived from the reaction using a reagent of formula Aa below:

wherein Ar is a di-substituted six-membered aromatic ring, in this case a benzene ring bearing two -CHO functions. Here the two functions -CHO are in positions para one with respect to the other. The reagent of formula Aa is 1,4-benzenedicarboxaldehyde.

The other reagent reacting with the reagent of formula Aa is a reagent of formula B:

H ₂ N Ri

in which R1 has the following formula:

in which R ₃ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical. In this case, R ₃ represents a monovalent radical chosen from the group consisting of the alkylene, arylene, arylalkylene, alkylarylene, cycloalkylene and alkenylene radicals, preferably from the group consisting of the alkylene and arylene radicals. Here, R ₃ represents the benzyl radical. The reagent of formula B is benzamide.

Compound C1 is prepared from 1,4-benzenedicarboxaldehyde (CAS 23-27-8) and benzamide (CAS 55-21-O) in a polar solvent. Thus, for example, 20 g of benzamide are dissolved in 250 ml of water. 11 g of 1,4-benzenedicarboxaldehyde are then added. The mixture is mixed at 100 ° C. for 4 hours with stirring until the compound C1 is precipitated. The reaction mixture is then filtered and washed 5 times consecutively with 100 mL of boiling water to remove the benzamide residues and The final product is finally recovered and dried in an oven for 48 hours at 70.degree. 20 g of compound C1 are obtained in the form of a beige powder. Compound C2 precursor of the aldehyde of the composition 12

The compound C2 is derived from the reaction using a reagent of formula Aa below:

H ₂ N R

in which R1 has the following formula:

wherein R3 is NH ₂ . The reagent of formula B is urea.

Due to the presence of two -NH ₂ groups on the reagent of formula B, the products of the reaction are numerous. Among them are the main reaction products of the following formulas

2b It may also be mentioned products of minority reactions among which we find the reaction product of formula C2c below:

Compound C2 is prepared in a manner analogous to compound C1 from 1,4-benzenedicarboxaldehyde (CAS 23-27-8) and urea (CAS 57-13-6).

[0235] Compound C3 precursor of the aldehyde of the composition 13

The compound C3 is derived from the active ingredient of formula Aa below:

H ₂ N Ri

in which R 1 represents a monovalent radical selected from the group consisting of alkyl, aryl, AL-NH ₂ radicals with AL representing a monovalent alkyl radical, AR-NH ₂ with AR representing a monovalent aryl radical, AL-NR ₂ H with AL representing a monovalent alkyl radical and AR-NR ₂ H with AR representing a monovalent aryl radical. In this case, R 1 represents an AL-NH ₂ radical with AL representing a monovalent alkyl radical, in this case a hexyl radical. :

B3

The reagent of formula B3 is hexane-1,6-diamine.

Due to the presence of two -NH ₂ groups on the reagent of formula B3, the products of the reaction are numerous. Among them, mention may be made of the main reaction products of the following formulas C3a, C3b:

[0240] It is also possible to mention products of minority reactions, of which one has a hole

C3c

Compound C3 is prepared in a manner analogous to compound C1 from 1,4-benzenedicarboxaldehyde (CAS 23-27-8) and hexane-1,6-diamine (CAS 124-). 09-4). [0242] Comparative tests

In a first step, the reinforcing filler was incorporated in an elastomer, by thermomechanically kneading the whole, until a maximum temperature of between 110 ° C. and 190 ° C. was reached. Then the whole was cooled to a temperature below 110 ° C. Then, in a second step, the crosslinking system, the aromatic polyphenol and the aldehyde or compound were incorporated. At the end of this second step, the mixture was heated to 150 ° C until the maximum rheometric torque was obtained in order to vulcanize the composition and crosslink the resin. Then, a characterization of the rigidity at 23 ° C. of the composition was carried out during a tensile test. Characterization of the delay phase and of the stiffness at high temperature - maximum rheometric torque

The measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983). The evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization and crosslinking of the resin. From the evolution of the rheometric torque, we determine the presence of a delay phase when the increase in the rheometric torque over 5 minutes of the tested composition is less than the increase in the rheometric torque over 5 minutes of a control composition comprising the same aromatic polyphenol and the corresponding aldehyde, here the T1 composition. The presence of such a delay phase is indicated in Table 1. FIGS. 2 to 4 show each curve representing the evolution of the rheometric torque respectively of the compositions 11 to 13 as well as those representing the evolution of the rheometric torque of the compositions T0 and T1.

The higher the maximum rheometric torque Cmax, the more the composition has a rigidity that can be maintained at high temperature.

Characterization of rigidity at 23 ° C. - Traction test

These tests make it possible to determine the elasticity stresses and the properties at break. Unless otherwise indicated, they are made in accordance with ASTM D 412 of 1998 (Test C). In second elongation (i.e. after an accommodation cycle), the so-called "nominal" secant moduli (or apparent stresses, in MPa) are measured at 10% elongation (denoted "MA10"). All these tensile measurements are carried out under the normal conditions of temperature and hygrometry, according to the standard ASTM D 1349 of 1999 and reported in Table 1. [0249] First, the results of Table 1 show that the use of an aromatic polyphenol and an aldehyde in the control composition T1 makes it possible to obtain a rigidity at 23 ° C. which is much higher than that of a composition without a reinforcing resin (T0). However, the T1 composition does not exhibit a retardation phase so that the phenol-aldehyde resin of the T1 composition cross-links early.

Each composition according to the invention 11 to 13 has a retardation phase and a rigidity which, although slightly lower than that of the composition T1 in certain examples described, is largely sufficient to allow a reinforcement of the rubber composition. In addition, this rigidity can be increased by modifying other parameters such as the levels of aromatic polyphenol and compounds used.

Each composition according to the invention 11 to 13 also has excellent stiffness performance at elevated temperatures and significantly improved compared to control compositions T0 and T1.

In addition, each composition 11 to 13 does not produce formaldehyde during its cooking, for example by crosslinking or vulcanization.

It will also be noted that the retardation phase and the rigidity at 23 ° C. can be chosen as functions of the application by varying the nature of R 1 and therefore the reagent of formula B to protect the aldehyde function (s).

The invention is not limited to the embodiments described above.

In other embodiments, it can thus be envisaged that the resin is based on one or more compounds and one or more aromatic polyphenols according to the invention and, in addition to these constituents, based on of one or more additional aldehydes and / or one or more additional aromatic polyphenols not in accordance with the invention.

Table 1

Composition Polyphenol aromatic Aldehyde Phase MA10 1 MPa) Cmax retardation (dN.m)

TO / I 14, 4, 25

T1 Phloroglucinol (1) 1,4-Benzenedicarboxaldehyde (2) No 53, 1 58

Composition Polyphenol Aromatic Compound Phase MA10 (MPa) Cmax retard (dN.m)

11 Phloroglucinol (1) Compound C1 Yes 49, 4 64

12 Phloroglucinol (1) Compound C2 Yes 47, 7 65

13 Phloroglucinol (1) Compound C3 Yes 51, 8 75

(1) Phloroglucinol (from Alfa Aesar, 99% pure);

(2) 1,4-benzenedicarboxaldehyde (from ABCR, 98% purity).

Claims

claims

1. Rubber composition, characterized in that it comprises at least one resin based on:

at least one compound derived from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N R- | R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

The rubber composition of claim 1, wherein Ar is a six-membered aromatic ring.

The rubber composition according to claim 2, wherein the remainder of the aromatic ring Ar is unsubstituted.

The rubber composition of claim 2, wherein the Ar aromatic ring is di-substituted.

5. The rubber composition according to the preceding claim, wherein the reagent A has the following formula Aa:

(Aa)

The rubber composition according to claim 4 or 5, wherein the two substituents of the aromatic ring Ar are in the para position with respect to each other.

The rubber composition according to any one of claims 2 to 6, wherein Ar is a benzene aromatic ring.

The rubber composition of claim 1, wherein Ar is a five-membered aromatic ring.

The rubber composition of claim 8 wherein the remainder of the aromatic ring Ar is unsubstituted.

10. A rubber composition according to the preceding claim, wherein the reagent of formula A has the following formula:

(Ab)

wherein X is N, S or O, preferably X is O.

1 1. The rubber composition of claim 8 wherein the aromatic ring Ar is di-substituted.

12. A rubber composition according to the preceding claim, wherein the reagent A has the following Ac formula:

wherein X is N, S or O, preferably X is O.

13. The rubber composition according to the preceding claim, wherein the reagent A has the following formula Ad:

(Ad)

wherein X is N, S or O, preferably X is O.

The rubber composition according to claim 1, wherein the reagent of formula A is selected from the group consisting of 1,4-benzenedicarboxaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these reagents.

A rubber composition according to any one of claims 1 to 14, wherein the radical R 1 represents a monovalent radical selected from the group consisting of alkyl, aryl, AL-NH ₂ radicals with AL representing a monovalent alkyl radical, AR -NH ₂ with AR representing a monovalent aryl radical, AL-NR ₂ H with AL representing a monovalent alkyl radical and AR-NR ₂ H with AR representing a radical monovalent aryl, preferably in the group consisting of AL-NH ₂ radicals with AL representing a monovalent alkyl radical, AR-NH ₂ with AR representing a monovalent aryl radical, AL-NR ₂ H with AL representing a monovalent alkyl radical and AR -NR ₂ H with AR representing a monovalent aryl radical.

16. A rubber composition according to any one of claims 1 to 14, wherein the radical Ri has the following formula:

The rubber composition according to claim 16, wherein R ₃ represents a monovalent radical selected from the group consisting of alkylene, arylene, arylalkylene, alkylarylene, cycloalkylene, alkenylene, preferably from the group consisting of alkylene and arylene radicals. .

18. The rubber composition according to claim 16, wherein the radical R 1 is selected from the group consisting of the radicals of the following formulas:

The rubber composition according to any one of claims 1 to 14, wherein the radical R 1 has the following formula:

in which R ₃ is NH ₂ .

20. A rubber composition according to any one of the preceding claims, wherein the radical R ₂ represents a monovalent radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl and alkenyl radicals.

21. Rubber composition, characterized in that it comprises at least one resin based on: at least one aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted, and

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Z ₂ represents a divalent radical of following formula:

22. The rubber composition of claim 21, wherein Ar is a six-membered aromatic ring.

23. The rubber composition of claim 22 wherein the remainder of the aromatic ring Ar is unsubstituted.

24. The rubber composition according to claim 22, wherein the aromatic ring Ar is di-substituted.

25. A rubber composition according to the preceding claim, wherein the compound is selected from the group consisting of the compounds of the following formulas:

(Nia) (IVa) (Va)

and their mixtures.

26. A rubber composition according to claim 24 or 25, wherein the two substituents of the aromatic ring Ar are in the para position with respect to each other.

27. The rubber composition according to any one of claims 22 to 26, wherein Ar is a benzene aromatic ring.

28. The rubber composition of claim 21, wherein Ar is a five-membered aromatic ring.

29. The rubber composition of claim 28 wherein the remainder of the aromatic ring Ar is unsubstituted.

30. A rubber composition according to the preceding claim, wherein the aromatic ring Ar has the formula

wherein X is N, S or O, preferably X is O.

31. The rubber composition of claim 28, wherein the aromatic ring Ar is di-substituted.

32. A rubber composition according to the preceding claim, wherein the compound is selected from the group consisting of compounds of the following formulas:

(IIIb) (IVb) (Vb)

and their mixtures.

33. The rubber composition according to the preceding claim, wherein the aromatic ring Ar has the formula

wherein X is N, S or O, preferably X is O.

34. A rubber composition according to the preceding claim, wherein the two substituents of the aromatic ring Ar are in position 2 and 5 with respect to each other.

35. A rubber composition according to any one of the preceding claims, wherein the aromatic ring of the aromatic polyphenol carries three hydroxyl functions in the meta position relative to one another.

36. A rubber composition according to any one of the preceding claims, wherein the two ortho positions of each hydroxyl function are unsubstituted.

37. A rubber composition according to any one of the preceding claims, wherein the remainder of the aromatic ring of the aromatic polyphenol is unsubstituted.

38. A rubber composition according to any one of the preceding claims, wherein the aromatic polyphenol comprises a plurality of aromatic rings, at least two of which are each carrying at least two hydroxyl functions in the meta position with respect to the other, the two ortho positions of at least one of the hydroxyl functions of at least one aromatic ring being unsubstituted.

39. A rubber composition according to the preceding claim, wherein at least one of the aromatic rings of the aromatic polyphenol carries three hydroxyl functional groups in the meta position relative to one another.

40. The rubber composition of claim 38 or 39, wherein the two ortho positions of each hydroxyl function of at least one aromatic ring are unsubstituted.

41. A rubber composition according to any one of claims 38 to 40, wherein the two ortho positions of each hydroxyl function of each aromatic ring are unsubstituted.

42. A rubber composition according to any one of the preceding claims, wherein each aromatic ring of the aromatic polyphenol is a benzene ring.

The rubber composition according to any one of claims 1 to 42, wherein the aromatic polyphenol is selected from the group consisting of resorcinol, phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, , 2 ', 4,4'-tetrahydroxybenzophenone, and mixtures of these compounds, preferably the aromatic polyphenol is phloroglucinol.

44. The rubber composition according to any one of claims 1 to 42, wherein the aromatic polyphenol is a pre-condensed resin based on:

at least one polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions in the meta position with respect to each other, the two ortho positions of at least one of the hydroxyl functional groups being unsubstituted, and

- At least one compound capable of reacting with the polyphenol comprising at least one aldehyde function and / or at least one compound capable of reacting with said aromatic polyphenol comprising at least two hydroxymethyl functions carried by an aromatic ring.

A rubber composition according to any one of the preceding claims comprising a diene elastomer selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and these elastomers.

46. A rubber composition according to any one of the preceding claims in the fired state.

47. A rubber composition according to any one of the preceding claims comprising a residue obtained from the radical and / or Z ₂ .

48. A rubber composition, characterized in that it comprises:

at least one compound derived from the reaction between a reagent of formula A: (AT)

and a reagent of formula B and / or C:

H

H ₂ N Ri R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

49. A rubber composition, characterized in that it comprises:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Zi represents a monovalent radical chosen from the radicals of the following formulas: Z ₂ represents a divalent radical of following formula

50. A rubber composition according to claim 48 or 49 in the green state.

51. Process for the manufacture of a rubber composition in the green state, characterized in that it comprises a mixing step:

at least one compound derived from a reagent of formula A:

(AT)

and a reagent of formula B and / or C: H ₂ N Ri R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

52. Process for manufacturing a rubber composition in the green state, characterized in that it comprises a mixing step:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Z ₂ represents a divalent radical of following formula:

The method of claim 51 or 52, comprising the steps of:

- cool the assembly to a temperature below 1 10 ° C;

- mix at a temperature below 1 10 ° C.

54. Process for producing a rubber composition in the cooked state, characterized in that it comprises:

(AT)

and a reagent of formula B and / or C H ₂ N Ri R ₂ N Ri

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

each radical R1, R2 represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical,

- Then, a shaping step of the rubber composition in the green state,

then, a step of crosslinking the rubber composition during which a resin based on the aromatic polyphenol and the compound is crosslinked.

55. A method of manufacturing a rubber composition in the cooked state, characterized in that it comprises:

(i) (II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

Zi represents a monovalent radical chosen from the radicals of the following formulas: Z ₂ represents a divalent radical of following formula:

in which each radical R 1, R ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical,

- Then, a shaping step of the rubber composition in the green state,

56. A rubber composition, characterized in that it is obtainable by a method according to one of claims 51 to 55.

57. Use of a composition between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H ₂ N R- | R ₂ N Ri

(B) (C) in which :

Ar represents an aromatic ring, optionally substituted,

58. Use of a compound resulting from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

H

H ₂ N Ri R ₂ N Ri

(B) (C)

in which :

Ar represents an aromatic ring, optionally substituted,

59. A rubber composite reinforced with at least one reinforcement element embedded in a rubber composition, characterized in that the rubber composition is according to any one of claims 1 to 50 or claim 56.

60. Pneumatic tire (1), characterized in that it comprises a rubber composition according to any one of claims 1 to 50 or according to claim 57 or a rubber composite according to the preceding claim.