WO2018015676A1

WO2018015676A1 - High-strength rubber composition

Info

Publication number: WO2018015676A1
Application number: PCT/FR2017/051991
Authority: WO
Inventors: Anne-Lise THUILLIEZ; David DOISNEAU; 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
Also published as: FR3054231B1; FR3054231A1

Abstract

The invention relates to a rubber composition comprising at least one resin based on: A1) a compound from the reaction between a reagent of formula A and a reagent of formula B and/or C in which Ar represents an optionally substituted aromatic core, and each radical M₁, M₂ is, independently from each other, a hydrocarbonated monovalent radical or a substituted hydrocarbonated monovalent radical; and A2) a derivative of an aromatic polyphenol comprising at least one aromatic core carrying at least two -O-Z groups in meta position in relation to each other, the two ortho positions of at least one of the -O-Z groups being non-substituted, Z being different from hydrogen.

Description

High stiffness rubber composition

The invention relates to rubber compositions, a method of manufacturing such compositions, a rubber composite and a tire.

It is known to use in some tire parts, rubber compositions having 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.

[0003] High rigidity can be obtained by using a so-called concentrated vulcanization system, that is to say comprising, in particular, relatively high levels of sulfur and vulcanization accelerator.

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.

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

[0007] High rigidity may otherwise be obtained by increasing the rate of reinforcing filler.

However, in known manner, increasing the stiffness of a rubber composition by increasing the load ratio may 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.

Conventionally, the increase in rigidity is obtained by incorporating reinforcing resins based on an acceptor / methylene donor system. 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 network reinforcing filler / elastomer 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.

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

The methylene acceptors conventionally used in tire rubber compositions are precondensed phenolic resins.

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 invention aims to provide a stiffened rubber composition by means of compounds with low environmental impact.

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

A1) of at least one compound derived from the reaction between a reagent of formula A:

(AT)

and a formulation reagent

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted, each Μ-ι radical, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical; and A2) of at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of the -OZ groups being unsubstituted, Z being different from hydrogen.

The name "derivative of aromatic polyphenol" is used because of the existing structural similarity between the aromatic polyphenol derivative and the corresponding aromatic polyphenol. Indeed, the aromatic polyphenol derivative has a structure similar to that of the corresponding aromatic polyphenol but in which the hydrogen of at least two hydroxyl functions is replaced by the radical Z. Thus, the aromatic polyphenol derivative has a general formula ( V1) below:

(V1)

wherein Ar is the aromatic ring.

Unexpectedly, the Applicants have discovered during their research that the A1 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 an A1 compound could, with an aromatic polyphenol derivative, form an alternative resin to the reinforcing resins based on a methylene acceptor / donor system.

In addition, the combination of the compound A1 and the aromatic polyphenol derivative A2 according to the invention makes it possible to obtain rubber compositions having a rigidity at low deformation equivalent to or even greater than conventional rubber compositions which comprise donors. methylene HMT or H3M and with respect to the rubber compositions lacking a reinforcing resin.

In addition, the A1 compounds and derivatives of aromatic polyphenols A2 according to the invention also prevent early crosslinking of the resin. Indeed, a problem related to the use of certain reinforcing resins, in particular that based on the aromatic polyphenol corresponding to the derivative 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, by 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. Thanks to the invention, the resin formed from the compound A1 and the aromatic polyphenol derivative A2 is formed less rapidly than from the corresponding aldehyde A and aromatic 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. From the comparison of the evolution of the rheometric pairs of a first composition comprising the derivative of the aromatic polyphenol A2 and the compound A1 and of a second composition comprising the corresponding aromatic polyphenol and / or aldehyde A, it can be seen that the derivative of aromatic polyphenol A2 and the compound A1 makes it possible to delay the crosslinking of the resin with respect to the direct reaction between the corresponding aromatic polyphenol and the aldehyde A.

The inventors at the origin of the invention hypothesize that the aromatic polyphenol derivative A2 is a precursor of the aromatic polyphenol and that the latter makes it possible to avoid early crosslinking of the resin because of the Z radical of each -OZ group that is different from hydrogen. Indeed, the radical Z of each -O-Z group would act as a temporary protective group allowing, according to the hypothesis of the inventors, the formation of a hydroxyl function under predetermined reaction conditions and therefore the formation of the corresponding aromatic polyphenol. 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 group -O-Z and are easily determinable, or 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.

The -OZ group is such that the reaction between the derivative of the aromatic polyphenol and the A1 compound allows the crosslinking of the resin. Preferably, the group -OZ is such that the reaction between the derivative of the aromatic polyphenol and the compound A1 allows the crosslinking of the resin under the same reaction conditions, preferably the same reaction temperature conditions, as a resin based on corresponding aromatic polyphenol (having hydroxyl groups in place of -OZ groups) and aldehyde A. Typically, the temperature is greater than or equal to 120 ° C, preferably greater than or equal to 140 ° C. Similarly, the inventors at the origin of the invention hypothesize that the compound A1 is a precursor of the aldehyde (which would be the aldehyde of formula A) and that compound A1 allows avoid early crosslinking of the resin due to 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.

The reactants of formulas B and C are such that the reaction between the derivative of the aromatic polyphenol A2 and the compound A1 allows the crosslinking of the resin. Preferably, the reactants of formulas B and C are such that the reaction between the derivative of the aromatic polyphenol A2 and the compound A1 allows the crosslinking of the resin under the same reaction conditions, preferably the same temperature reaction conditions, as phenol-aldehyde resin based on the corresponding aromatic polyphenol and aldehyde (that is to say 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 compounds A1 and derivatives of the aromatic polyphenols A2 according to the invention also make it possible to maintain the rigidity of the composition at high temperatures, in particular for temperatures up to 150 ° C. Indeed, the resin formed from the compound A1 and the aromatic polyphenol derivative A2 has an improved temperature resistance compared to a resin formed from the aldehyde of formula A and the aromatic polyphenol derivative A2. This temperature resistance can be determined by measuring the evolution of the rheometric torque as a function of time as described above. The aromatic polyphenol derivative A2 and the compound A1 make it possible to obtain an extremely high torque value demonstrating excellent stiffness maintenance with increasing temperature.

As already explained above, the inventors at the origin of the invention hypothesize that the compound A1 is a precursor of the aldehyde of formula A and that the aromatic polyphenol derivative A2 is a precursor of the corresponding aromatic polyphenol. As already explained above, this combination makes it possible to avoid an immediate crosslinking of the resin due to a reaction that would generate, off-line, the aldehyde function from the compound A1 and the hydroxyl functions from the aromatic polyphenol derivative. A2. Indeed, the reagents of formulas B) and C) and the group -OZ act as reagents and temporary protective groups allowing, according to the hypothesis of the inventors, the formation of at least one aldehyde function and hydroxyl functions under conditions predetermined reactions (in other words the regeneration of the aldehyde of formula A and the aromatic polyphenol corresponding to the derivative). The time taken to regenerate the aldehyde of formula A and the aromatic polyphenol, even if it is very short, for example of the order of one minute, would allow a better dispersion of the compound A1 and the aromatic polyphenol derivative A2 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 to understand a resin comprising the mixture and / or the reaction product of the various basic constituents used for the final condensation of this resin, some of them. which may be intended to react or capable of reacting with one another or with their surrounding chemical environment, at least in part, during the various phases of the process for manufacturing the composition, the composites or the tire, in particular during a step of cooking. 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.

According to the invention, the basic constituents therefore comprise at least one compound A1 and at least one aromatic polyphenol derivative A2. In one embodiment, the base components may comprise other additional additional components of the compound A1 and the aromatic polyphenol derivative A2. In another embodiment, the basic constituents consist of at least one compound A1 and at least one aromatic polyphenol derivative A2.

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 / - Ν, Ν ', Ν''- trimethylolmelamine, hexamethylolmelamine, N-methylolmelamine, Ν, Ν'-dimethylolmelamine, N, N', N '' - tris (methoxymethyl) melamine, N, N ', N '' - tributyl-N, N ', N "-trimethylolmelamine More advantageously, these other additional components are free of formaldehyde and devoid of the methylene donors described in this paragraph.

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; 2, F ₃ , F ₄ and F ₅ are chosen, independently of one another, 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.

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

By lacking 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) A1 in the basic constituents is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

By lacking 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) A1 in the basic constituents. is less than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

By "meta position relative to each other", it will be understood that the target groups, for example the -OZ groups in the aromatic polyphenol, are borne by carbons of the aromatic ring separated from one another. another by a single other carbon of the aromatic nucleus.

By "position para one with respect to the other", it will be understood that the groups referred to are opposite to 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 one group is a position opposite to the group on the 6-membered aromatic ring bearing the group.

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. . Similarly, the "ortho position" with respect to one group is the position adjacent to the group on the aromatic ring bearing the group.

By "link" of a nucleus, we will hear a constituent atom of the nucleus skeleton. Thus, for example, a benzene ring comprises six members, each member being a carbon atom. In another example, a furan ring comprises five members, four members each being a carbon atom and the remaining member being an oxygen atom.

In the context of the invention, the "compound A1" designates the compound defined in paragraph 1.1. This compound will also be designated "A1 compound"

The "aromatic polyphenol derivative A2" in the context of the invention refers to the aromatic polyphenol derivative defined in paragraph I.2. This compound will also be referred to as "A2 aromatic polyphenol derivative"

According to the designation "aromatic polyphenol", the aromatic ring bearing at least two hydroxyl functions meta position relative to each other, the two ortho positions of at least one of the hydroxyl functions being non substituted is a benzene ring.

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 may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass.

The rubber composition therefore comprises at least one (that is to say one or more) resin; this resin being based on at least one (that is to say one or more) compound A1 and at least one (that is to say one or more) derived from aromatic polyphenol A2, which constituents will be described in detail below.

Preferably, the aromatic polyphenol derivative is obtained by a manufacturing process in which the following are reacted:

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

a compound making it possible to form the -O-Z group from each hydroxyl function.

In some preferred embodiments, all -O-Z groups are identical. However, in other embodiments, at least two -O-Z groups are different.

The invention also relates to a rubber composition comprising at least one resin based on:

A1) of at least one compound selected from the group consisting of compounds of the following formulas:

(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:

M ₂

Z ₂ represents a divalent radical of following formula

in which each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, and

A2) of at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one -OZ groups being unsubstituted, Z being different from hydrogen.

In contrast to 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 reagents of formulas A and B and / or C.

The invention also relates to a rubber composition comprising: A1) at least one compound derived from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical; and A2) at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of the -OZ groups being unsubstituted, Z being different from hydrogen.

Another object of the invention is a rubber composition comprising:

A1) at least one compound selected from the group consisting of compounds of the following formulas:

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

in which :

Ar represents an aromatic ring, optionally substituted,

M ₂

Z ₂ represents a divalent radical of following formula

A2) at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of the groups -OZ being unsubstituted, Z being different from hydrogen.

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

(AT)

and a reagent of formula B and / or C:

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical; and A2) of at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of the -OZ groups being unsubstituted, Z being different from hydrogen.

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 rubber composition in the green state comprising a mixing step:

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

in which :

Ar represents an aromatic ring, optionally substituted,

M ₂

Z ₂ represents a divalent radical of following formula

in which each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical; and

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

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

(AT)

and a reagent of formula B and / or C:

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical; and A2) of at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of the -OZ groups being unsubstituted, Z being different from hydrogen,

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

and then, a step of crosslinking, for example by vulcanization or baking, of the rubber composition during which a resin based on the aromatic polyphenol derivative A2 and the compound A1 is crosslinked.

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

A1) of 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-i represents a monovalent radical chosen from the radicals of the following formulas:

M ₂

Z ₂ represents a divalent radical of following formula:

in which each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical; and o A2) of at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two groups -O-

Z in the meta position relative to each other, the two ortho positions of at least one of the -O-Z groups being unsubstituted, Z being different from hydrogen,

- 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 derivative and the compound is crosslinked.

As explained above, the inventors theorize that during the crosslinking step, for example by vulcanization or firing, it is carried out, prior to the crosslinking of the resin:

a step of forming the aldehyde of formula A starting from compound A1 by forming, on the aromatic nucleus, at least one aldehyde function,

a step of forming the aromatic polyphenol from the derivative or precursor of the aromatic polyphenol A2 by forming, on the aromatic nucleus, at least two hydroxyl functional groups in the meta position with respect to each other, the two ortho positions at least one of the hydroxyl functions being unsubstituted, each hydroxyl function being obtained from each -OZ group, and

a step of crosslinking a resin from the aromatic polyphenol and from the aldehyde of formula A.

Still another object of the invention is a rubber composition obtainable by a method as described above.

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

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

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.

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.

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 (ie, 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 ".

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.

1.1 - Reaction Product A1 Between Reagents A and B and / or C - Compound A1 of the Rubber Composition

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, which compound constitutes a first essential constituent of the resin and the composition according to the invention.

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 formaldehyde rubber compositions because of the environmental impact of these compounds and recent regulatory developments, including European regulations, on this type of compound.

In one embodiment, Ar is an aromatic six-membered ring. By "link" of a ring, one will hear a constituent atom of the core skeleton. 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.

In a first variant of this embodiment of a six-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. For example, in this first variant, when the six-membered aromatic ring is a benzene ring, the aldehyde generated from the compound is benzaldehyde.

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

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

(Aa)

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

(Nia) (IVa) (Va)

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

Advantageously, the two substituents of the aromatic ring Ar are in para position with respect to each other. By "position relative to each other", it will be understood that the functions referred to are opposite each other, that is to say in positions 1 and 4 of the aromatic ring at 6 links. 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.

Preferably, Ar is a benzene aromatic ring.

In another embodiment, Ar is an aromatic five-membered ring. In a manner analogous to the definition given above, the term "link" of a ring, will mean a constituent atom of the core skeleton. 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.

In a first variant of this embodiment of a 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.

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.

In this first variant, the aromatic ring Ar therefore has the following formula:

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

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

(Ab1)

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 the monovalent alkylene, arylene arylalkylene, alkylarylene, cycloalkylene and alkenylene radicals.

In another embodiment, X comprises S. Advantageously, X represents S, SR ₅ , SR ₅ R ₅ ', S = 0 or O = S = O with R ₅ , R ₅ ' representing, independently, one on the other, a radical selected from the group consisting of monovalent radicals alkylene, arylene arylalkylene, alkylarylene, cycloalkylene and alkenylene.

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

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

(Aa ')

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

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

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

(Ac)

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

In this second variant, the aromatic ring Ar thus preferably has the following formula:

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

Even more preferably, the reagent of formula A has the following Ad formula:

(Ad)

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

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.

When X represents O, the reagent of formula Ad is 2,5-furanedicarboxaldehyde.

Thus, more preferably, the reagent of formula A is chosen from the group consisting of 1,4-benzene-dicarboxaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these reagents.

Preferably, the composition is free of formaldehyde and / or free of methylene donor selected from the group consisting of hexa-methylenetetramine (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.

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

wherein Q represents an alkyl group containing from 1 to 8 carbon atoms; 2, F ₃ , F ₄ and F ₅ are chosen, independently of one another, 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.

Even 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.

By lacking 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 by the total weight of the compound (s) A1 in the composition is lower than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

By lacking 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 A1 compound (s) in the composition is lower than or equal to 10%, preferably 5%, more preferably 2% and even more preferably 1%.

In one embodiment, the M-ι radical 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-NM ₂ H with AL representing a monovalent alkyl radical and AR-NM ₂ H with AR representing a monovalent aryl radical. In this embodiment, the 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, reagent C can therefore be an amine secondary (alklyl and aryl radicals), a secondary diamine (radicals AL-NM ₂ H and AR NM ₂ H) or a diamine comprising a primary amine function and a secondary amine function.

Preferably, the M-ι radical represents a monovalent radical chosen from the group consisting of the radicals AL-NH ₂ with AL representing a monovalent alkyl radical, AR-NH ₂ with AR representing a monovalent aryl radical, AL-NM ₂ H with AL representing a monovalent alkyl radical and AR-NM 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.

More preferably, 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.

In another embodiment, the radical M-ι has the following formula:

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

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

In a second variant, the M-ι radical 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.

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.

In yet another embodiment, the radical M-ι has the following formula:

in which M ₃ represents NH ₂ .

In this other embodiment, the reagent B is urea.

Advantageously, the radical M ₂ represents a monovalent radical chosen from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl and alkenyl radicals.

Advantageously, each radical Mi, M ₂ is devoid of reactive function with respect to an aromatic polyphenol derivative A2. 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 Mi, M ₂ is, for example, devoid of aldehyde and hydroxymethyl function.

I.2 - Derivative of aromatic polyphenol A2

The second essential component of the resin is an aromatic polyphenol derivative A2 having one or more aromatic ring (s). The aromatic polyphenol derivative comprises at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of these -OZ groups being unsubstituted .

According to the invention, the aromatic polyphenol derivative A2 can be, in one embodiment, a single molecule of aromatic polyphenol derivative comprising one or more aromatic nuclei, at least one of these aromatic nuclei, or even each nucleus. aromatic, carrying at least two groups - OZ in the meta position relative to each other, the two ortho positions of at least one of these -OZ groups being unsubstituted.

Such simple molecules do not include a repeating pattern.

According to the invention, the aromatic polyphenol derivative A2 can 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 unsubstituted ; and

at least one compound capable of reacting with said aromatic polyphenol comprising at least one aldehyde function, for example an aromatic aldehyde bearing at least one aldehyde functional group, 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,

the hydroxyl functions of the pre-condensed resin remaining reactive at the end of the condensation of the pre-condensed resin being substituted with -O-Z groups.

The hydroxyl functions remaining reactive are those that are capable of reacting to form the -O-Z group, they are also those capable of reacting with aromatic polyphenol derivative A2. The -O-Z groups will form after deprotection, ie after release of the temporary protective group, hydroxyl functions that may be involved in the condensation reaction of the pre-condensed resin with the compound A1.

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 identical or different groups and each independently representing a hydroxyl function or a -OZ group, these two groups being in the meta position with respect to the other, the two ortho positions of at least one of these groups being unsubstituted. In this embodiment, in order to form the aromatic polyphenol derivative A2 in the form of pre-condensed resin, the precondensed resin based on an aromatic polyphenol comprising at least one aromatic ring bearing at least two hydroxyl functions is formed. In the meta position with respect to each other, the two ortho positions of at least one of the OH hydroxyl functions being unsubstituted, and this pre-condensed resin is reacted with a compound making it possible to form the group; OZ from each remaining hydroxyl function reactive at the end of the condensation of the pre-condensed resin.

In another embodiment, the aromatic polyphenol derivative A2 is a mixture of a derivative of an aromatic polyphenol forming a single molecule and a pre-condensed resin based on aromatic polyphenol in which the hydroxyl functions of the pre-condensed resin remaining reactive at the end of the condensation of the pre-condensed resin are substituted with -OZ groups.

In the particular embodiments which follow, the aromatic nucleus (s) of the aromatic polyphenol derivative are described. For the sake of clarity, the "aromatic polyphenol derivative" is described in its single molecule form. The aromatic polyphenol at the origin of the corresponding derivatives can then be condensed and partly define the repetitive pattern. The characteristics of the pre-condensed resin are described in more detail below.

In a preferred embodiment, the aromatic ring of the aromatic polyphenol derivative carries three -O-Z groups in the meta position with respect to each other.

Preferably, the two ortho positions of each -O-Z group are unsubstituted. By this is meant that the two carbon atoms located on both sides (in the ortho position) of the carbon atom carrying the -O-Z group carry a single hydrogen atom.

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

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

In a preferred embodiment, at least one of the aromatic nuclei of the aromatic polyphenol derivative carries three -O-Z groups in the meta position relative to one another.

[0124] Preferably, the two ortho positions of each -O-Z group of at least one aromatic ring are unsubstituted.

Even more preferentially, the two ortho positions of each -OZ group of each aromatic ring are unsubstituted. Advantageously, each aromatic ring of the aromatic polyphenol derivative is a benzene ring.

By way of example of an aromatic polyphenol derivative comprising a single aromatic ring, mention may be made in particular of the resorcinol and phloroglucinol derivatives of formula (IV) and (V):

(IV) (V)

By way of example, in the case where the aromatic polyphenol derivative comprises several aromatic nuclei, at least two of these aromatic nuclei, which are identical or different, are chosen from those of general formulas:

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

Another example of an aromatic polyphenol derivative is a derivative of 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, derivative having the following structural formula (VII):

(VII)

Another example of an aromatic polyphenol derivative is a derivative of 2,2 ', 4,4'-tetrahydroxydiphenyl benzophenone, derivative of the following structural formula (VIII):

(VIII)

It is noted that each compound VII and VIII is an aromatic polyphenol derivative comprising two aromatic rings (of formulas VI-c) each of which carries at least two (in this case two) -OZ groups in position. meta with respect to each other.

Note that in the case of a derivative of an aromatic polyphenol having at least one aromatic ring according to the formula VI-b, the two ortho positions of each -OZ group of at least one aromatic ring are not substituted. In the case of a derivative of an aromatic polyphenol having a plurality of aromatic rings according to the formula VI-b, the two ortho positions of each -O-Z group of each aromatic ring are unsubstituted.

According to one embodiment of the invention, the aromatic polyphenol derivative is chosen from the group consisting of a resorcinol derivative (IV), a derivative of phloroglucinol (V), a derivative of 2,2 ', 4 , 4'-Tetrahydroxydiphenyl sulfide (VII), a derivative of 2,2 ', 4,4'-tetrahydroxybenzophenone (VIII) and mixtures thereof. In a particularly advantageous embodiment, the aromatic polyphenol derivative is a derivative of phloroglucinol (V).

In one embodiment, the aromatic polyphenol derivative comprises a pre-condensed resin based on an aromatic polyphenol as described in any one of these embodiments, the hydroxyl functions of the pre-condensed resin remaining reactive. upon condensation of the pre-condensed resin being substituted with -OZ groups.

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

The compound capable of reacting with said aromatic 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 functional groups carried by an aromatic nucleus and reacting with said aromatic polyphenol may be a compound A1 as defined above in paragraph 1.1, a compound of formula Ar- (CHO) ₂ , where Ar is as defined above for the compound A1 of paragraph 1.1, or any other aldehyde. Advantageously, the compound capable of reacting with said aromatic polyphenol comprising at least one aldehyde function and / or the compound capable of reacting with said aromatic polyphenol comprising at least two hydroxymethyl functions carried by an aromatic ring is chosen from the group consisting of 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, formaldehyde, benzaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde 1,4-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,2-benzenedicarboxaldehyde and mixtures thereof. Very advantageously, when the compound capable of reacting with said aromatic polyphenol 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 function hydroxymethyl, this compound is selected 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 comprises at least one aromatic ring bearing at least two identical or different groups and each independently representing a hydroxyl function or a -OZ group, these two groups being in the meta position relative to each other, at least one of the carbon atoms of the aromatic ring, which was unsubstituted prior to condensation of the pre-condensed resin, being 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 likely to be able to react with a compound A1 according to the invention in a subsequent step. The aromatic polyphenol derivative A2 may also comprise a mixture of a free molecule of aromatic polyphenol derivative and a pre-condensed resin based on aromatic polyphenol, the hydroxyl functions of the pre-condensed resin remaining reactive to the result of the condensation of the pre-condensed resin being substituted with -OZ groups. In particular, the aromatic polyphenol derivative A2 may also comprise a mixture of phloroglucinol derivative and a precondensed phloroglucinol resin, the hydroxyl functions of the pre-condensed resin remaining reactive at the end of the condensation of the resin. pre-condensed being substituted with -OZ groups.

The following definitions of the -O-Z group apply as well to the aromatic polyphenol derivative in its single molecule or pre-condensed resin form.

[0141]

Advantageously, each -OZ group is chosen from the group consisting of -O-Si (RiR ₂ R ₃ ), -O-C ((= O) (R ₄ )) and -O-C (( = 0) (N (R ₅ R ₆ ))). Each group R 1, R ₂ , R 3 and R ₄ represents, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical. Each R ₅ and R ₆ represents, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical. Advantageously, as a temporary protecting group, each -OZ group has no reactive function with respect to compound A1. In the various embodiments described, each radical R 1, R ₂ , R ₃ , R ₄ , R 5 and R ₆ has no reactive function with respect to compound A1.

As a temporary protective group, each -OZ group is preferably devoid of reactive function vis-à-vis the other constituents of the rubber composition. In the various embodiments described, each radical R 1, R ₂ , R ₃ , R ₄ , R 5 and R ₆ is preferably free of reactive function with respect to the other constituents of the rubber composition.

By reactive function is meant here a function that would react under reaction conditions necessary for the regeneration of the aromatic polyphenol and under reaction conditions necessary for the crosslinking of the resin. Thus, each -OZ group is devoid of reactive function with respect to the aldehyde and hydroxymethyl functions. In the various embodiments described, each radical R 1, R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is devoid of a reactive function with respect to the aldehyde and hydroxymethyl functions.

In one embodiment, each -OZ group represents a group -O- Si (R- | R ₂ R ₃ ) with R 1, R ₂ , R ₃ representing, independently of one another, a radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl, alkenyl. Preferably, each R 1, R ₂ and R ₃ represents, independently of one another, a radical chosen from the group consisting of methyl, ethyl, propyl, phenyl, allyl and vinyl radicals, and even more preferentially a chosen radical. in the group consisting of methyl, ethyl, propyl, butyl, allyl, vinyl.

In the foregoing embodiments, the propyl radicals include radicals of formula -C ₃ H ₇ . These radicals are n-propyl and isopropyl.

In the foregoing embodiments, the butyl radicals include radicals of formula -C ₄ H ₉ . These radicals are n-butyl, isobutyl, sec-butyl and tert-butyl.

In the foregoing embodiments, the aryl radicals include aromatic rings from which a hydrogen atom has been removed. For example, the aryl radical is the radical C ₆ H ₅ obtained from benzene C ₆ H ₆ . Another exemplary aryl radical is C ₄ H ₃ 0 obtained from furan C ₄ H ₄ 0.

In the embodiment in which each -OZ group represents a group -O-Si (R ₁ R ₂ R 3), the aromatic polyphenol derivative may be such that R ₁ = R 2 = R ₃ = CH ₃ and has the formula (1) following:

(1)

The derivative (1) is prepared from phloroglucinol (CAS 108-73-6) and trimethylsilyl chloride (CAS 75-77-4) in the presence of an organic base. Thus, for example, 40 g of phloroglucinol are dissolved in 800 ml of chloroform. Next, 109 g of triethylamine are then added. Then 107 g of trimethylsilyl chloride CISi (CH ₃ ) ₃ are added dropwise to the reaction medium at room temperature. The whole is left at room temperature with stirring for 3 hours. The reaction mixture is then acidified with an aqueous solution of 37% hydrochloric acid. Then, two washes are carried out with water. The final product is finally recovered after drying over anhydrous sodium sulphate, filtration and evaporation of the solvent. 150 g of the derivative (1) are obtained in the form of a brown liquid. ( ¹ H NMR (CDCl ₃ , 300 MHz): 6.03 (3H, s), 0.27 (27H, s)).

In the embodiment in which each -OZ group represents a -O-Si group (RiR ₂ R3), the aromatic polyphenol derivative may be such that

R ₃ = CH = CH 2 and has the following formula 2):

(2)

The derivative (2) is prepared in a manner analogous to the derivative (1) from phloroglucinol (CAS 108-73-6) and dimethylvinylsilyl chloride (CAS 1719-58-0). ( ¹ H NMR (CDCl 3, 300 MHz): 6.15-5.60 (9H, m), 5.89 (3H, s), 0.15 (18H, s)).

In the embodiment in which each -OZ group represents a -O-Si group (RiR ₂ R 3), the aromatic polyphenol derivative may be such that

2 = ₃ = C ₆ H ₆ and has the following formula (3):

(3)

The derivative (3) is prepared in a manner analogous to the derivative (1) from phloroglucinol (CAS 108-73-6) and methyldiphenylsilyl chloride (CAS 144-79-6). ( ¹ H NMR (CDCl 3, 300 MHz): 7.70-7.30 (30H, m), 6.03 (3H, s), 0.59 (9H, s)).

In another embodiment, each -OZ group represents a group -O-C ((= O) (R ₄ )) with R ₄ representing a radical chosen from the group consisting of alkyl, aryl and arylalkyl radicals. , alkylaryl, cycloalkyl, alkenyl. Preferentially, R ₄ represents a radical chosen from the group consisting of methyl, ethyl and propyl, butyl, allyl, vinyl.

In this embodiment, the aromatic polyphenol derivative may be such that R ₄ = CH ₃ and has the following formula (4) (CAS 2999-40-8):

(4)

The derivative (4) is prepared from phloroglucinol (CAS 108-73-6) and acetyl chloride (CAS 75-36-5) in the presence of an organic base. Thus, for example, 18 g of phloroglucinol, 64 g of triethylamine are dissolved in 450 ml of tetrahydrofuran. 45 g of acetyl chloride are then added dropwise to the reaction medium at room temperature. The whole is left at room temperature with stirring for 3 hours. Then, the reaction medium is filtered and the tetrahydrofuran evaporated. The product is then dissolved in chloroform and an acid extraction is carried out followed by extraction with clear water. The final product is finally recovered after drying over anhydrous sodium sulphate, filtration and evaporation of the solvent. 36 g of the derivative are obtained in the form of a yellow powder. ( ¹ H NMR (CDCl ₃ , 300 MHz): 6.85 (3H, s), 2.28 (9H, s)).

In this embodiment, the aromatic polyphenol derivative may be such that and has the following formula (5):

(5)

The derivative (5) is prepared in a manner analogous to the derivative (4) from phloroglucinol (CAS 108-73-6) and stearolyl chloride (CAS 112-76-5). ( ¹ H NMR (CDCl3, 300 MHz): 6.84 (3H, s), 2.47 (6H, t), 1.87-1.16 (90H, m) 0.90 (9H, t)).

In this embodiment, the derivative of the aromatic polyphenol composition 16 is such that

and has the following formula (6):

(6)

The derivative (6) is prepared in a manner analogous to the derivative (4) from phloroglucinol (CAS 108-73-6) and lauroyl chloride (CAS 112-16-3). ( ¹ H NMR (CDCl3, 300 MHz): 6.83 (3H, s), 2.54 (6H, t), 1.84-1.62 (6H, m), 1.28 (48H, m), 0.90 (9H, t)). -

In yet another embodiment, each -OZ group represents a group -O-C ((= O) (N (R ₅ R ₆ ))) with R ₅ , R 6 representing, independently of one of the another, a radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl, alkenyl and hydrogen. Preferably, each R ₅ , R ₆ represents, independently of one another, a radical selected from the group consisting of methyl, ethyl, propyl, butyl, allyl, vinyl and hydrogen.

In this embodiment, the aromatic polyphenol derivative may be such that R ₅ = H and R ₆ = C ₆ H ₆ and has the following formula 7):

(7)

The derivative (7) is prepared from phloroglucinol (CAS 108-73-6) and isocyanate phenyl (CAS 103-71-9). In a two-necked flask are introduced 5 g (0.040 mol) of phloroglucinol and 30 ml of dioxane. The mixture is stirred at room temperature and 14.18 g (0.119 mol) of phenyl isocyanate are added via a dropping funnel. At the end of the addition, 200 mg of dibutyltin dilaurate are added. The temperature is raised to 80 ° C. for a period of 8 hours. At the end of the reaction, the dioxane is evaporated off under reduced pressure and then the final product is dried in a vacuum oven. The final product is a white powder obtained with a yield of 94%. ( ¹ H NMR (DMSO-d6, 300 MHz): 7.00-6.05 (15H, m), 6.24 (3H, s)). Γ01651 Rubber compositions according to the invention

Depending on the use of the composition, a quantity of aldehyde A1 ranging from 0.1 to 25 phr will be used. Similarly, use will be made of a quantity of aromatic polyphenol derivative A2 ranging from 0.1 to 25 phr.

In certain embodiments, the [aldehyde A1]: [aromatic polyphenol A2] molar ratio advantageously varies from 3: 1 to 1: 1, advantageously from 3: 1 to 1.5: 1.

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.

[0169] 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 of 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 (s) being be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.

[0173] 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, there may be mentioned 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 its 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 under 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 such as described below.

As reinforcing inorganic fillers are particularly suitable inorganic fillers of the siliceous type, in particular of silica (SiO ₂ ), or of the aluminous type, in particular of alumina (Al ₂ O ₃ ). The silica used may be any reinforcing silica known to those skilled in the art, especially any precipitated or pyrogenated silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / boy Wut. 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. "Silicone" silica EZ150G from PPG, "Zeopol" silicas 8715, 8745 and 8755 from Huber, silicas with a high specific surface area as described in 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, it would be possible to use a reinforcing filler of another nature, in particular organic, since 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 within 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.

[0185] 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 oils. of extension, whether these are of aromatic or non-aromatic nature, pigments, protective agents such as anti-ozone waxes, anti-ozonants chemicals, anti-oxidants, anti-fatigue agents or even promoters of accession.

[0187] Preferably, the rubber composition comprises a crosslinking system, more preferably a vulcanization system.

The vulcanization system comprises a sulfur donor agent, for example sulfur.

[0189] Preferably, the vulcanization system comprises vulcanization activators such as zinc oxide and stearic acid.

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, in particular 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 sulphenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazyl sulphenamide (abbreviated "TBBS"), N-tert-butyl-2-benzothiazyl sulphenimide (abbreviated "TBSI"), zinc dibenzyldithiocarbamate (in abbreviated "ZBEC") and mixtures of these compounds. Preferably, a primary accelerator of the sulfenamide type is used.

[0194] In one embodiment, the rubber composition is in the fired state, that is, vulcanized. In other embodiments, the composition is in the green, i.e. uncured, state, the crosslinked resin having been added later. to the unvulcanized composition.

In some embodiments, the composition comprises a residue obtained from the -Z radical of each -O-Z group. Prior to the crosslinking of the resin, and as supposed by the inventors at the origin of the invention, after formation of each hydroxyl function, each radical Z of each -O-Z group can make it possible to obtain a residue generated in situ. 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:

A1) at least one compound derived from the reaction between a reagent of formula A:

(AT)

and a reagent of formula B and / or C:

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

In this embodiment, the compound resulting from the reaction between the reagents 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,

M ₂

Z ₂ represents a divalent radical of following formula

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

[0199] Preferably, in this embodiment, the composition is in the green state, that is to say unvulcanized.

[0200] Preferably, the rubber composition can 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 derivative of the aromatic polyphenol A2 and to the compound A1 of the composition comprising the resin also apply to the composition comprising the derivative of the aromatic polyphenol A2 and the compound A1 not crosslinked in the state. of resin. [0202] 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, the two terms being synonymous) according to the invention 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 yarns 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 selected from the group consisting of monofilaments (or unitary 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 yarn or 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 strip 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 predominantly (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 the steel, more preferably carbonaceous pearlitic (or ferrito-pearlitic) steel advantageously comprising between 0.4% and 1.2% by weight of carbon.

The metal reinforcing element may 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:

or by twisting: the metal monofilaments or the strands undergo both a collective twist and an individual twist around their own axis, which generates a torque of untwisting 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.

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 metallic wire elements 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.

[0220] 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 vehicle of the heavy vehicle type.

[0223] This tire 1 comprises a crown 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 wrapped around the two rods 5 in each bead 4, the upturn 8 of this reinforcement 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 one bead to the other so as to form an angle between 80 ° and 90 ° with the plane medial circumferential (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 reinforcement 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 cooked state (after firing). [0225] 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 is not there 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 with respect to reagent A. Molar excess means that once the reaction is complete, at least 10% of the reaction is left behind. 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. [0229] Process for producing the aromatic polyphenol derivative

In the embodiment in which each -OZ group represents a group -O-Si (Ri R ₂ R 3), the following are reacted:

a compound of formula LG-Si (R ₁ R ₂ R ₃ ) with R 1, R ₂ and R ₃ representing, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical and LG representing a nucleofugal group.

The conditions of the reaction between the aromatic polyphenol and the compound of formula LG-Si (R ₁ R ₂ R ₃ ) are well known to those skilled in the art. For example, the process is carried out by first reacting, in an organic solvent, the aromatic polyphenol with a base, more preferably an organic base, and then introducing the compound of formula LG-Si (Ri R ₂ R ₃ ) in the reaction mixture. Depending on the groups R 1 _, R _2, and R ₃ and the aromatic polyphenol, the reaction is conducted between 20 ° C and 50 ° C for a few hours, for example between 1 hour and 10 hours.

In the embodiment in which each -OZ group represents a group

we react:

a compound of formula

with R 1 representing a hydrocarbon radical or a substituted hydrocarbon radical comprising at least two carbon atoms and

LG representing a nucleofuge group.

In the foregoing embodiments, the LG nucleofuge group represents a halogen. It is recalled that the halogens correspond to the elements F, Cl, Br and I. More preferably, LG represents chlorine.

[0234] Method of 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 can 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 1 10 ° 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, during a second step, incorporating a crosslinking system, the aromatic polyphenol derivative A2 and the compound A1;

- 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 derivative A2 and the aldehyde A1. 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 A1. and the aromatic polyphenol derivative A2. 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, we proceed to a crosslinking step, by example by vulcanization or baking of the composition, the composite or the blank during which the resin is based on the aromatic polyphenol derivative A2 and aldehyde A1. The crosslinking step, here of vulcanization or baking, 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.

[0242] In another embodiment, the method comprises the following steps:

- Incorporating into an elastomer, during a first step, a reinforcing filler, the derivative of 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.

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

[0244] Examples of embodiment of the invention and comparative tests

[0245] These tests demonstrate that:

the rigidity of the compositions according to the invention is greatly increased compared to a composition devoid of reinforcing resin,

the maintenance of the rigidity of the rubber composition according to the invention at elevated temperatures, in particular for temperatures up to 150 ° C., is greatly improved with respect to a composition devoid of reinforcing resin and with respect to a resin reinforcer crosslinked directly from the aromatic polyphenol and / or the corresponding aldehyde (aldehyde A),

- The resin of the composition according to the invention using compound A1 is free of formaldehyde and does not generate during its formation.

For this, several rubber compositions, hereinafter noted T0 to T4, 11 and 12 were prepared as indicated above and are summarized in Table 1 attached below.

All the compositions T0 to T4, 11 and 12 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 carbon black N326, 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 comprise any reinforcing resin added to this part. common.

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

In addition to the common part, the composition T2 comprises a phloroglucinol resin and the compound C1 forming a precursor of an aromatic aldehyde, here 1,4-benzenedicarboxaldehyde (molar proportions: 1 (phloroglucinol) / 1 (compound)). The T2 composition comprises 14 phr of phloroglucinol.

In addition to the common part, the composition T3 comprises a phloroglucinol resin and compound C2 forming a precursor of an aromatic aldehyde, here 1, 4-benzenedicarboxaldehyde (molar proportions: 2 (phloroglucinol) / 1 (compound)). The composition T3 comprises 14 phr of phloroglucinol.

[0252] In addition to the common part, the composition T4 comprises a resin based on phloroglucinol derivative 1 and 1,4-benzenedicarboxaldehyde (molar proportions: 1 (aromatic polyphenol derivative) / 1 (aldehyde)). The composition T4 comprises 14 phr of phloroglucinol derivative 1.

In addition to the common part, the composition 11 comprises a resin based on phloroglucinol derivative 1 and compound C1 (molar proportions: 1 (aromatic polyphenol derivative) / 1 (compound)). Composition 11 comprises 14 phr of Phloroglucinol derivative 1.

In addition to the common part, the composition 12 comprises a resin based on phloroglucinol derivative 1 and compound C2 (molar proportions: 2 (aromatic polyphenol derivative) / 3 (compound)). Composition 11 comprises 14 phr of phloroglucinol derivative 1.

The compositions T0 to T4 are not in accordance with the invention contrary to the compositions 11 and 12 which are in accordance with the invention.

In the green state, each rubber composition 11 and 12 according to the invention comprises:

at least one compound derived from the reactive reagent of formula A:

(AT)

and a formulation reagent

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

in which :

Ar represents an aromatic ring, optionally substituted,

each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, and

at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of the groups; OZ being unsubstituted, Z being different from hydrogen.

In the cooked state, each rubber composition 11 and 12 according to the invention comprises a resin based on:

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

(AT)

and a formulation reagent

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic nucleus, optionally substituted,

each Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical, and - at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position relative to each other, the two ortho positions of at least one of the -OZ groups being unsubstituted, Z being different from hydrogen.

[0258] Aromatic polyphenol derivative of the compositions T4, 11 and 12

The aromatic polyphenol derivative of the composition 11 is such that R ₁

and has the following formula (1):

Yes Yes

\ \

(1)

The derivative (1) is prepared following the protocol described above in the description.

[0261] Compounds C1 and C2

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:

(II) and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

M ₂

Z ₂ represents a divalent radical of following formula

[0263] 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 ring, and wherein Z-ι is selected from the radicals of the following formulas:

in which Μ-ι has the following formula:

in which M ₃ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical. In the present case, M 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, M 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: in which M-ι has the following formula

in which M ₃ represents a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical. In the present case, M 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, M ₃ represents the benzyl radical. The reagent of formula B is benzamide.

The compound C1 is prepared from 1,4-benzenedicarboxaldehyde (CAS 23- 27-8) and benzamide (CAS 55-21-0) in a polar solvent. Thus, for example, 20 g of benzamide are dissolved in 250 ml of water. 11 g of 1,4-benzene dicarboxaldehyde are then added. The mixture is mixed at 100 ° C. for 4 hours with stirring until the compound C1 is precipitated. Then, the reaction mixture is filtered and washed 5 times consecutively with 100 ml of boiling water in order to remove residues of benzamide and 1,4-benzenedicarboxaldehyde. The final product is finally recovered and then dried in an oven for 48 hours. at 70 ° C. 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:

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: in which M-ι 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-NM ₂ H with AL representing a monovalent alkyl radical and AR-NM ₂ H with AR representing a monovalent aryl radical. In this case, M-ι represents an AL-NH ₂ radical with AL representing a monovalent alkyl radical, in this case a hexyl radical. The reagent has the following formula B2:

The reagent of formula B2 is hexane-1,6-diamine.

Due to the presence of two -NH ₂ groups on the reagent of formula B2, the products of the reaction are numerous. Among them, mention may be made of the main reaction products of the following formulas C2a, C2b:

2b

[0274] Mention may also be made of products of minority reactions, among which are

Compound C2 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). [0276] Comparative tests

In a first step, the reinforcing filler was incorporated into 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 or the aromatic polyphenol derivative and the aldehyde or compound are 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.

[0278] Characterization of the delay phase and of the high temperature rigidity - 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, the presence of a delay phase is determined 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 aromatic polyphenol and the corresponding aldehyde, here the composition T1. The presence of such a delay phase is indicated in Table 1. FIGS. 2 and 3 show each curve representing the evolution of the rheometric torque of each composition 11 and 12 as well as those representing the evolution of the rheometric torque of the compositions T0 to T4.

[0280] 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 elastic 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 (ie 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. First of all, the results in Table 1 show that the composition T1 comprising a resin based on an aromatic polyphenol and an aromatic aldehyde has a rigidity at 23 ° C. and a temperature withstand of this rigidity. much higher than that of a composition devoid of reinforcing resin (T0). Nevertheless, this composition T1 does not exhibit a delay phase so that the resin of the composition T1 crosslinks early.

The compositions T2, T3 and T4 have a rigidity at 23 ° C. and a resistance to stiffness at elevated temperatures (Cmax) improved compared to the compositions T0 and T1, in particular because of the aromatic polyphenol derivative (T4). or the compound (T2, T3). In addition, unlike the composition T1, the compositions T2, T3 and T4 have a delay phase to prevent early crosslinking of the resin. Nevertheless, the composition T4 has a rigidity at 23 ° C. less than the composition T1.

The compositions 11 and 12 according to the invention have a lag phase. In addition, the composition 11 has a rigidity at 23 ° C higher than that of the composition T4 and the composition 12 has a rigidity at 23 ° C equivalent or greater than those of all the control compositions. The rigidity at high temperatures (Cmax) of the compositions 11 and 12 according to the invention is greatly improved compared to all those of the control compositions.

In addition, each composition 11, 12 according to the invention does not produce formaldehyde during its cooking, for example by crosslinking or vulcanization.

It will also be noted that the retardation phase and the stiffness at 23 ° C. can be chosen according to the application by varying the -O-Z groups and the compounds B and C.

The invention is not limited to the embodiments described above.

In other embodiments, it may be envisaged that the resin is based on one or more compounds A1 and one or more aromatic polyphenol derivatives A2 according to the invention and, in addition to these constituents. , based on one or more additional aldehydes not in accordance with the invention and / or one or more additional aromatic polyphenols not in accordance with the invention. Table 1

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

(9) 1,4-Benzenedicarboxaldehyde (from ABCR, 98% pure)

Claims

claims

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

(AT)

and a reagent of formula B and / or C:

(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:

(Ac)

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.

15. A rubber composition according to any one of claims 1 to 14, wherein the radical M-ι represents a monovalent radical chosen from the group consisting of alkyl, aryl, AL-NH ₂ radicals with AL representing a monovalent radical. alkyl, AR-NH ₂ with AR representing a monovalent aryl radical, AL-NM ₂ H with AL representing a monovalent alkyl radical and AR-NM ₂ H with AR representing a monovalent aryl radical, preferably in the group consisting of the radicals AL -NH ₂ with AL representing a monovalent alkyl radical, AR-NH ₂ with AR representing a monovalent aryl radical, AL-NM ₂ H with AL representing a monovalent alkyl radical and AR-NM 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 M-ι has the following formula:

The rubber composition according to claim 16, wherein M 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 M-ι radical is chosen 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 M-ι radical has the following formula:

in which M ₃ represents NH ₂ .

20. A rubber composition according to any one of the preceding claims, wherein the radical M 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:

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

in which :

Ar represents an aromatic nucleus, 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 derivative carries three -O-Z groups in the meta position with respect to each other.

36. A rubber composition according to any one of the preceding claims, wherein the two ortho positions of each -O-Z group 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 derivative is unsubstituted.

38. A rubber composition according to any one of the preceding claims, wherein the aromatic polyphenol derivative comprises a plurality of aromatic rings, at least two of which are each bearing at least two -O-Z groups in the meta-metal position. With respect to each other, the two ortho positions of at least one of the -OZ groups of at least one aromatic ring being unsubstituted.

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

40. A rubber composition according to any one of claims 1 to 39, wherein the aromatic polyphenol derivative is selected from the group consisting of resorcinol, phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl derivatives. sulfide, 2,2 ', 4,4'-tetrahydroxybenzophenone and mixtures of these compounds.

41. A rubber composition according to any one of claims 1 to 39, wherein the aromatic polyphenol derivative is a pre-condensed resin based on:

at least one compound capable of reacting with said aromatic 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 functional groups carried by an aromatic nucleus,

42. A rubber composition according to any one of the preceding claims, wherein each -OZ group is selected from the group consisting of -O-Si (R ₁ R ₃ R ₃ ), -O-C ((= O) ( R ₄ )), -O-C ((= O) (N (R ₅ R ₆ ))), with each group R 1, R ₂ , R ₃ and R ₄ represents, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical and each R ₅ and R ₆ represents, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical.

43. The rubber composition according to any one of claims 1 to 42, wherein each -OZ group represents a group -O-Si (RiR ₂ R 3) with R 1, R ₂ , R 3 representing, independently of one of the other, a radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl, alkenyl.

44. The rubber composition according to any one of claims 1 to

42, wherein each -OZ group represents a group -O-C ((= O) (R ₄ )) with R ₄ representing a radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl, alkenyl radicals .

A rubber composition according to any one of claims 1 to 42, wherein each -OZ group represents a group -O-C ((= O) (N (R ₅ R ₆ ))) with R ₅ , R ₆ represents, independently of one another, a radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl, alkenyl and hydrogen.

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.

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

48. A rubber composition according to any one of the preceding claims comprising a residue obtained from the Z radical of each -O-Z group.

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

(AT)

and a reagent of formula B and / or C:

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

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

A1) at least one compound selected from the group consisting of 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

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

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

(AT)

and a reagent of formula B and / or C:

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

53. 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 52 or 53, comprising the steps of:

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

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

- mix at a temperature below 1 10 ° C.

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

(AT)

and a reagent of formula B and / or C:

(B) (C)

and mixtures of these compounds,

in which :

Ar represents an aromatic ring, optionally substituted,

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

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

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

in which :

Ar represents an aromatic ring, optionally substituted,

-

M

Z ₂ represents a divalent radical of following formula:

in which each radical Mi, M ₂ represents, independently of one another, a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical; and A2) of at least one derivative of an aromatic polyphenol comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one at least one of the -OZ groups being unsubstituted, Z being different from hydrogen,

- 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 derivative and the compound is crosslinked.

57. A rubber composition, characterized in that it is obtainable by a process according to any one of claims 52 to 55.

58. 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 51 or claim 57.

59. Pneumatic tire (1), characterized in that it comprises a rubber composition according to any one of claims 1 to 51 or according to claim 57 or a rubber composite according to the preceding claim.