Process for preparation of elastomeric compositions comprising linear or cyclic dicarboxylic acids

Abstract

The present invention relates to an improved process for the preparation of elastomeric compositions comprising linear or cyclic dicarboxylic acids or derivatives thereof.

Description

Technical Field

[0001] The present invention relates to an improved process for preparing an elastomeric composition comprising a linear or cyclic dicarboxylic acid or a derivative thereof. Prior Art

[0002] A distinctive feature of elastomeric composites is entropy elasticity, which occurs above the glass transition temperature of the elastomer and is the basis of their properties. Dienic elastomers, i.e., elastomers having unsaturated moieties in the main chain, such as poly(1,4-cis-butadiene) and poly(1,4-cis-isoprene), are characterized by a large mobility of the main chain, which is attributed to the ease with which the polymer chains rotate around the single bonds close to the unsaturated moieties. When crosslinking the polymer chains of these unsaturated elastomers, the composite material acquires the property of entropy elasticity. However, despite their outstanding elasticity, elastomeric composites do not have the mechanical properties required for demanding applications, such as those in tire compounds. To achieve these properties, the composite material must be loaded with reinforcing fillers.

[0003] Since the beginning of the twentieth century, carbon black has been used as a reinforcing filler for elastomeric composites. Due to the addition of carbon black, both the static and dynamic mechanical properties of the elastomeric composites increase. However, carbon black also causes a significant increase in the hysteresis of the elastomeric composites, and thus a significant increase in energy dissipation. In fact, it is well known that the elastic modulus of a composite material filled with carbon black (where a sinusoidal stress has been applied to the composite material) decreases, from the minimum strain up to a strain of about 25% (the limit estimated for linear behavior). This phenomenon is called the "Payne Effect" and is an indicator of the energy dissipation of the material.

[0004] To have mechanical reinforcement and low energy dissipation, silica is used instead of carbon black or together with carbon black as a reinforcing filler. Due to the use of a coupling agent, usually a silane containing sulfur atoms, a chemical bond is established between the silica and the elastomer chains, which results in a reduction in hysteresis and energy dissipation. Therefore, despite the disadvantages associated with its use, the use of silica has increased sharply in the past few decades.

[0005] In fact, silica causes an increase in the viscosity of the compound, a deterioration in processability, and a shortening of the storage time of the composite material. These disadvantages stem from the surface activity of silica: the polar groups promote extensive supramolecular interactions. Notably, the shorter storage time leads to the need for a specific plan for the production of the compound and the procedures for storing and transporting the compound, which has a significant impact on logistics.

[0006] In addition, in order to achieve effective mixing of silica-based composites, specific and expensive mixing equipment is required. Due to the use of silanes, silica-based compounds increase the adhesion to the metal parts of the mixer, and this requires special treatment of the metal surface. Finally, silica is corrosive and abrasive, and this also requires special treatment of the metal surface and modification of the maintenance procedures.

[0007] These drawbacks are relevant on an industrial scale, for example when silica-based elastomeric composites are used in tire compounds. However, tire compounds, especially those for tire treads, are generally almost entirely based on silica as a reinforcing filler, and an increasing amount of research effort is being made to use silica to partially replace carbon black, also in tire compounds other than tire treads. Research work has also been carried out to use silica as the sole filler in tire compounds other than tire treads. This is because the main aim is to reduce the energy dissipation of rolling tires, and at least in the existing prior art, this aim has never been achieved with carbon black as the sole reinforcing filler.

[0008] In fact, several attempts have been made to reduce the Payne effect caused by carbon black, for example by optimizing its dispersion in the elastomeric matrix, separating the aggregates and / or elemental particles therefrom, covering them with an elastomeric layer. The applicant has reported different ways to achieve this by using preformed adducts between sp 2 hybrid carbon allotropes and pyrrole derivatives or other suitable compounds (see for example WO 2016 / 050887, WO 2020 / 225595A1, WO2020 / 222103). However, attempts to partially or fully replace silica have not been reported so far.

[0009] Another key issue is that the reaction between the elastomeric composition (such as a tire compound) and oxygen and ozone under normal operating conditions leads to a change in the chemical structure of the polymer chains. The reaction with oxygen leads to the introduction of oxygen-containing functional groups in the polymer chains, which detrimentally affect the properties of the elastomer. The reaction with ozone is particularly harmful because it leads to chain breakage.

[0010] Quinoline (a heterocyclic aromatic organic compound containing a nitrogen atom) is generally used as an antioxidant in tire compounds. Typical examples of quinoline used for these applications are 1,2-dihydro-2,2,4-trimethylquinoline (TMQ), an oil-based substance, which is classified as acutely toxic when swallowed and causes severe eye irritation.

[0011] Paraphenylenediamines, organic compounds containing primary, secondary or tertiary amino groups, are commonly used as antioxidants and antiozonants. The most commonly used paraphenylenediamine in tire compounds is N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), a known sensitizer that is harmful if swallowed and may cause allergic skin reactions. Summary of the invention

[0012] Applicants have addressed the need for a process for preparing an elastomeric composition which at least partially overcomes the above-mentioned disadvantages.

[0013] In particular, the Applicant has solved the problem of providing an elastomeric composition capable of achieving a balance between the advantages offered by both silica and carbon black while overcoming the associated disadvantages. Furthermore, the Applicant has solved the problem of providing an elastomeric composition that effectively prevents reactions with oxygen and ozone and has a reduced content of toxic and hazardous chemicals.

[0014] The Applicant has also solved the problem of obtaining such an elastomeric composition with a simple technology (with reduced environmental impact) and using standard solid-state mixing techniques used in the tire industry.

[0015] Surprisingly, the Applicant has found that these results can be achieved by a simplified process that relies on the addition of a linear or cyclic dicarboxylic acid or a derivative thereof directly within the elastomeric composition, thereby avoiding the preparation of a sp 2 By this method, the Applicant has obtained elastomeric compositions having optimal dynamic mechanical properties at least comparable to those usually obtained by a two-step preparation and to those obtained using silica as reinforcing filler, while having the processability and the above-mentioned advantages associated with the use of carbon black.

[0016] Furthermore, Applicants have surprisingly discovered that linear or cyclic dicarboxylic acids or derivatives thereof suitable for the direct preparation of elastomeric compositions can also provide antioxidant and antiozonant properties, thereby replacing the more toxic chemical compounds commonly used as antioxidants and antiozonants.

[0017] The process according to the invention makes it possible to obtain elastomeric compositions exhibiting low hysteresis and reduced Payne effect, with consequent reduced energy dissipation, while conferring prolonged resistance to the action of oxygen and ozone, and which are particularly suitable as compounds for tyres.

[0018] According to a first aspect, the present invention relates to a method for preparing an elastomeric composition comprising a compound represented by the following formula (I):

[0019]

[0020] The compound of formula (I) can be linear or cyclic, and when the compound is linear, the symbol (C) does not represent a bond, and when the compound is cyclic, the symbol (C) represents a bond;

[0021] m, v, p, q, r, u and n can independently be equal to 1 or equal to 0; and

[0022] X1 and Y can be O or NR7;

[0023] and wherein:

[0024] R7 is selected from: hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl; and

[0025] if X1 and Y are NR7, then:

[0026] -R1, R6 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl;

[0027] if X1 and Y are O, then:

[0028] -R1, R6 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl, alkali metal, alkaline earth metal, transition metal, or

[0029]

[0030] wherein R8, R9, R 10 、R 11 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl;

[0031] and wherein:

[0032] R2, R3, R4, and R5 are independently selected from: hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl;

[0033] and wherein:

[0034] - When the compound of formula (I) is a linear compound:

[0035] n is 1 and v and / or m is 1;

[0036] The symbols (A) and (B) independently represent a single bond or a double bond, and

[0037] if the symbol (A) is a double bond, then p and v are 0 and m is 1, or p and m are 0 and v is 1;

[0038] if the symbol (B) is a double bond, then q and r are 0 and u is 1, or q and u are 0 and r is 1;

[0039] if the symbol (A) is a single bond, then p, v, and m are 1;

[0040] if the symbol (B) is a single bond, then q, r, and u are 1; and

[0041] - When the compound of formula (I) is a cyclic compound:

[0042] The symbols (A) and (B) are double bonds, m, v, p, q, n, and u are 0 and r is 1, or m, v, p, q, n, and r are 0 and u is 1;

[0043] The method comprises the following steps:

[0044] a) providing one or more elastomers, a compound of formula (I), and at least one reinforcing filler; and

[0045] b) performing at least one mixing step.

[0046] It is noted that in step a), the compound of formula (I) is provided as such together with one or more elastomers. Thus, in the method according to the invention, no premixing step is carried out between the compound of formula (I) and the at least one reinforcing filler. Brief Description of the Drawings

[0048] A description is shown herein with reference to the drawings, which are provided by way of example only and do not limit the invention.

[0049] Figure 1Shows the 3,4,5-triacetoxy-6-carbonyl-tetrahydro-pyran-2-carboxylic acid (precursor) obtained as disclosed in Example 1 1 1H NMR spectrum (DMSO-d6, 400 MHz).

[0050] Figure 2 Shows the 3-hydroxy-2-carbonyl-2H-pyran-6-carboxylic acid (Compound 2) obtained as disclosed in Example 2 1 1H NMR spectrum (DMSO-d6, 400 MHz).

[0051] Figure 3 Shows the ethyl 3-hydroxy-2-carbonyl-2H-pyran-6-carboxylate (Compound 3) obtained as disclosed in Example 3 1 1H NMR spectrum (DMSO-d6, 400 MHz). Detailed Description

[0052] Definitions

[0053] According to this specification, the terms "carbon allotropes" and "carbon-based fillers" are used interchangeably and / or are both represented by the abbreviation CA.

[0054] For the purposes of this specification and the appended claims, the compounds of formulas (I) and (II) disclosed herein also include derivatives, such as esters, salts, enantiomers, diastereomers, preferably esters and salts.

[0055] Hereinafter, the term "elastomeric composition" is used to cover the sum of all components added during the preparation of an elastomeric mixture, regardless of the fact that these components are actually present simultaneously, whether they are introduced sequentially, or whether they can be traced in the elastomeric mixture or the final tire.

[0056] For the purposes of this specification and the following claims, the term "phr" (parts per hundred parts of rubber) represents the number of parts by weight of a defined component of an elastomeric composition / 100 parts by weight of an elastomeric polymer.

[0057] Detailed Description

[0058] According to a first aspect, the present invention relates to a method for preparing an elastomeric composition comprising a compound represented by the following formula (I):

[0059]

[0060] Wherein the compound of formula (I) can be linear or cyclic, and when the compound is a linear compound, the symbol (C) does not represent a bond, and when the compound is a cyclic compound, the symbol (C) represents a bond;

[0061] m, v, p, q, r, u, and n can independently be equal to 1 or equal to 0; and

[0062] X1 and Y can be O or NR7;

[0063] and wherein:

[0064] R7 is selected from: hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl; and

[0065] if X1 and Y are NR7, then:

[0066] - R1, R6 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl;

[0067] if X1 and Y are O, then:

[0068] - R1, R6 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl, alkali metal, alkaline earth metal, transition metal, or

[0069]

[0070] wherein R8, R9, R 10 、R 11 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl;

[0071] and wherein:

[0072] R2, R3, R4, R5 are independently selected from: hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl;

[0073] and wherein:

[0074] - when the compound of formula (I) is a linear compound:

[0075] n is 1, and v and / or m is 1;

[0076] The symbols (A) and (B) independently represent a single bond or a double bond, and

[0077] if the symbol (A) is a double bond, then p and v are 0 and m is 1, or p and m are 0 and v is 1;

[0078] if the symbol (B) is a double bond, then q and r are 0 and u is 1, or q and u are 0 and r is 1;

[0079] if the symbol (A) is a single bond, then p, v and m are 1;

[0080] if the symbol (B) is a single bond, then q, r and u are 1; and

[0081] - when the compound of formula (I) is a cyclic compound:

[0082] the symbols (A) and (B) are double bonds, m, v, p, q, n and u are 0 and r is 1, or m, v, p, q, n and r are 0 and u is 1;

[0083] The method comprises the following steps:

[0084] a) providing one or more elastomers, a compound of formula (I) and at least one reinforcing filler; and

[0085] b) performing at least one mixing step.

[0086] Preferably, the Y is O.

[0087] Preferably, the R1 and R6 are independently selected from hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, aryl.

[0088] Preferably, the R2-R5 are independently selected from hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl, aryl.

[0089] Preferably, in the compound of formula (I), the Y and X1 are O; the R1 and R6 are independently selected from hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl and aryl; and the R2-R5 are independently selected from hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl and aryl.

[0090] In one embodiment of the present invention, the compound of formula (I) is a compound represented by formula (II):

[0091]

[0092] wherein n is 1; and wherein the symbols (A) and (B) independently represent a single bond or a double bond, and

[0093] if the symbol (A) is a double bond, then p and v are 0 and m is 1, or p and m are 0 and v is 1;

[0094] if the symbol (B) is a double bond, then q and r are 0 and u is 1, or q and u are 0 and r is 1;

[0095] if the symbol (A) is a single bond, then p, v and m are 1;

[0096] if the symbol (B) is a single bond, then q, r and u are 1

[0097] and wherein X1, Y and R1-R6, when present, are as defined above.

[0098] Preferably, the compound of formula (II) is a compound represented by one of the following formulas (III)-(VII):

[0099]

[0100]

[0101] wherein n is 1; and X1, Y and R1-R6, when present, are as defined above.

[0102] In an alternative embodiment of the present invention, the compound of formula (I) is a compound represented by formula (VIII):

[0103]

[0104] wherein Y, X1, R1 and R5 are as defined above.

[0105] Preferably, in the compounds of formulas (II)-(VIII), when present, the Y and X1 are O; the R1 and R6 are independently selected from hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl and aryl; and the R2-R5 are independently selected from hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl and aryl.

[0106] In a particularly preferred embodiment of the present invention, the compounds of formulas (I)-(VIII) are selected from:

[0107]

[0108]

[0109] Preferably, the 2,5-dihydroxy muconic acid is a mixture of trans-trans, cis-trans and cis-cis isomers.

[0110] Typically, the compound of formula (I) is provided in an amount of at least 0.1 phr, preferably from 0.5 phr to 6 phr, even more preferably from 0.5 phr to 4 phr, such as from 0.5 phr to 2 phr, or from 0.99 phr to 2 phr.

[0111] Typically, at least one of the one or more elastomers provided in step a) of the process according to the invention is an unsaturated elastomer, which is preferably selected from the group consisting of: poly(1,4-cis-isoprene), natural rubber or synthetic polymers, poly(3,4-isoprene), poly(butadiene) (in particular poly(butadiene) having a high content of 1,4-cis units, i.e. poly(1,4-cis-butadiene)), isoprene / isobutene copolymers, halogenated isoprene / isobutene copolymers such as halogenated butyl rubber, in particular chlorinated butyl rubber and brominated butyl rubber, 1,3-butadiene / acrylonitrile copolymers, styrene / 1,3-butadiene copolymers, styrene / isoprene / 1,3-butadiene copolymers, styrene / 1,3-butadiene / acrylonitrile copolymers and mixtures thereof.

[0112] Advantageously, at least one elastomer of one or more monoolefins can be further provided. The monoolefins can be selected from: ethylene and 1-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or mixtures of these monoolefins.

[0113] The elastomer of one or more monoolefins can contain dienes, which generally have 4 to 20 carbon atoms and are preferably selected from: 1,3-butadiene, isoprene, 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, vinyl norbornene or mixtures of these dienes. The dienes can be optionally halogenated.

[0114] Among these elastomers of one or more monoolefins, the following are preferred: ethylene / propylene copolymers (EPR) or ethylene / propylene / diene copolymers (EPDM) and poly(isobutene).

[0115] Advantageously, in step a) of the process according to the invention, an unsaturated elastomer based on diene or non-diene monomers can be further provided, which is functionalized by reaction with a suitable terminator or coupling agent. In particular, the diene elastomer polymer can be obtained by anionic polymerization, which is promoted by an organometallic initiator (in particular an alkyl lithium), and terminated by reaction with a suitable terminator or coupling agent (such as an epoxide, a carbonyl compound (such as cyclohexanone and benzophenone), a substituted or unsubstituted imine, a carbodiimide, an alkyl tin halide, an alkoxysilane or an aryloxysilane).

[0116] Preferably, the at least one reinforcing filler is selected from the group consisting of: sp 2 Hybrid carbon allotropes, silica, layered silicates, mixed oxides of aluminum and magnesium having a layered structure, alumina, and silicoaluminates, and mixtures thereof.

[0117] Preferably, the sp 2 Hybrid carbon allotropes are selected from: carbon black, graphene, bilayer graphene, 3 to 10 layers of graphene, graphite, high surface area graphite, single-walled or multi-walled carbon nanotubes, longitudinally or helically extended carbon nanotubes, nanocones, nanohorns, nanotoroids, fullerenes, and mixtures thereof.

[0118] Even more preferably, the sp 2 Hybrid carbon allotropes are selected from: carbon black, graphene, graphite, high surface area graphite, single-walled or multi-walled carbon nanotubes, and mixtures thereof.

[0119] In a particularly preferred embodiment, the sp 2 Hybrid carbon allotrope is carbon black.

[0120] Generally, the sp 2 Hybrid carbon allotropes are provided in an amount of at least 1 phr, preferably 2 phr to 70 phr, even more preferably 3 phr to 50 phr, such as 10 phr to 50 phr, or 15 phr to 50 phr.

[0121] In an embodiment of the present invention, at least one reinforcing filler is selected from carbon black or a mixture of carbon black and silica. In such an embodiment, carbon black is provided in an amount of at least 10 phr, preferably at least 15 phr, even more preferably 30 phr to 70 phr.

[0122] In an embodiment of the present invention, silica is provided in an amount of 0 to 100 phr, preferably 0 to 50 phr, even more preferably 0 to 25 phr.

[0123] Thus, in the method according to the present invention, the total amount of the reinforcing filler provided can reach 10 to 150 phr, preferably 20 to 150 phr, even more preferably 30 to 80 phr.

[0124] In an embodiment of the present invention, one or more additives may be further provided in step a). The additives are selected based on the specific application of the composition and may be, for example, anti-aging agents, such as antioxidants and / or anti-ozone agents, plasticizers, binders, modified resins, coupling agents, or mixtures thereof.

[0125] In one embodiment of the present invention, in step a), at least one anti-aging agent selected from antioxidants, antiozonants, and mixtures thereof is provided.

[0126] In a particularly preferred embodiment, in step a), at least one antioxidant or at least one antiozonant is provided.

[0127] Generally, the antioxidant and the antiozonant are each independently provided in an amount of from 0.1 phr to 20 phr, preferably from 0.5 phr to 20 phr, either alone or in combination with each other.

[0128] A preferred antiozonant is 1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD).

[0129] A preferred antioxidant is 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ).

[0130] In particular, for the purpose of improving processability, a plasticizer, usually selected from mineral oils, vegetable oils, synthetic oils, or mixtures thereof (such as aromatic oil, naphthenic oil, phthalate, soybean oil, or mixtures thereof), may be added to the elastomeric composition. The amount of the plasticizer is generally from 0 phr to about 70 phr, preferably from about 5 phr to about 30 phr.

[0131] In an embodiment of the present invention, one or more vulcanizing agents may be further provided. The vulcanizing agent comprises a sulfur-based vulcanization system, which comprises sulfur or a sulfur-containing molecule (sulfur donor), together with vulcanization accelerators and / or activators known in the art.

[0132] Particularly effective activators are compounds of zinc, especially ZnO, ZnCO3, and zinc salts of saturated or unsaturated fatty acids containing 8 to 18 carbon atoms, such as zinc stearate, which is preferably formed in situ from ZnO and a fatty acid or a mixture thereof in the elastomeric composition.

[0133] Commonly used accelerators may be selected from: dithiocarbamates, guanidines, thioureas, thiazoles, sulfenamides, thiurams, amines, and xanthates, and mixtures thereof.

[0134] Preferred vulcanizing agents are, for example, stearic acid, ZnO, TBBS (N-tert-butyl-2-benzothiazolesulfenamide), and sulfur, or mixtures thereof.

[0135] According to a preferred embodiment, the vulcanizing agent is provided in an amount greater than or equal to about 1 phr, preferably greater than or equal to about 2 phr.

[0136] Preferably, the amount of the vulcanizing agent is less than or equal to about 20 phr, preferably less than or equal to about 10 phr.

[0137] Advantageously, the amount of sulfur is from about 0.5 phr to about 8 phr.

[0138] Typically, said at least one mixing step is carried out as follows: the polymer components are mixed together with the compound of formula (I) according to the invention, together with reinforcing fillers and other optional additives known in the art.

[0139] The mixing can be carried out, for example, using an open mixer of the "two-roll mill" type and / or a mixer with tangential rotors and / or a closed mixer of the type with intermeshing rotors (Intermix TM ) and / or in a continuous mixer of the Ko-Kneader TM type and / or twin-screw or multi-screw type and / or planetary type.

[0140] These components are generally not all introduced into the mixer simultaneously, but are usually added successively. In particular, the vulcanization additives, such as vulcanizing agents which may include activators and / or accelerators, are usually added in a step downstream of the introduction and processing of all the other components.

[0141] Generally, this is a further mixing step carried out according to known techniques, in particular using a sulfur-based vulcanization system which is usually used for diene elastomer polymers. For this purpose, in the material, after one or more thermo-mechanical treatment steps, a sulfur-based vulcanizing agent is introduced together with a vulcanization accelerator. In the final treatment step, the temperature is usually kept below 120 °C, preferably below 100 °C, to avoid any unwanted pre-crosslinking phenomenon.

[0142] Thus, in one embodiment, the method according to the invention further comprises the following steps:

[0143] c) providing one or more vulcanizing agents, which optionally contain activators and / or accelerators as disclosed above; and

[0144] d) carrying out a further mixing step.

[0145] The mixing step of the method according to the invention can be carried out at a temperature of from 40 °C to 130 °C.

[0146] In the curable elastomer composition, the individual components of the elastomer composition do not always remain unchanged or are individually traceable, since they can be completely or partially transformed by the influence of their interaction with other components or by the influence of the energy provided, such as heat and / or mechanical energy.

[0147] Experimental part

[0148] Materials

[0149] All reagents and solvents used for the preparation of pyranone derivatives, as well as adipic acid and muconic acid, were obtained from Sigma-Aldrich and used without further purification.

[0150] 1H-NMR spectra were recorded on samples dissolved in deuterated chloroform (CDCl3) and dimethyl sulfoxide (DMSO-d6). 1 1H-NMR spectra.

[0151] The elastomers used were:

[0152] - Poly(1,4-cis-isoprene) (NR), solid natural rubber SIR20, obtained from Eatern GR Thailand-Conburi. Mooney viscosity (ML(1+4)@100 °C): 73 MU;

[0153] - Poly(1,4-cis-butadiene) (butadiene rubber, BR) Europrene obtained from Polimeri Europa

[0154] - IR (isoprene rubber) SKI-3 obtained from Nizhnekamskneftekhim;

[0155] The sp 2 hybrid carbon allotropes used were:

[0156] - Carbon black N326 obtained from Birla Carbon;

[0157] - Carbon black N550 obtained from Birla Carbon

[0158] Other components for preparing the elastomer composition:

[0159] - X50S (bis(triethoxysilylpropyl) polysulfide), obtained from Evonik;

[0160] - Silica from grade 1165MP, obtained from Solvay;

[0161] - Stearic acid obtained from Undesa;

[0162] - ZnO obtained from Zincol Ossidi;

[0163] - 6PPD ((1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine) Santoflex TM , obtained from Eastman;

[0164] -TBBS (N-tert-butyl-2-benzothiazolylsulfenamide) NZ / EGC - obtained from Lanxess;

[0165] - sulfur obtained from International Sulphur Inc;

[0166] - TMQ (2,2,4-trimethyl-1,2-dihydroquinoline) NAUGARD Q obtained from CHEMTURA CORPORATION;

[0167] - Resins: Escorez 1102 obtained from Exxon mobilWax; Riowax obtained from SER corporation.

[0168] Characterization

[0169] Pyrone derivatives obtained by NMR spectral analysis. Recorded using a Bruker 400MHz (100MHz 13 C) instrument operating at 298K 1 1H-NMR and 13 13C-NMR spectra. Chemical shifts are expressed in parts per million (ppm), with the solvent residue peak as the internal standard (DMSO-d6:

[0170] δ = 2.50 ppm, CDCl3: δ = 7.26 ppm).

[0171] Thermogravimetric analysis (TGA) is a quantitative analysis technique that provides the weight loss of a material as a function of time and temperature. In other words, the material is heated under a given heating condition and can undergo transformations that result in the partial or complete loss of the material itself into the gas phase. TGA is carried out using a Mettler TGA SDTA / 851 instrument under flowing air (60 mL / min). The sample (10 mg) is heated from 25 °C to 400 °C at 10 °C / min and held at 400 °C for 20 min.

[0172] Differential scanning calorimetry (DSC) was performed under flowing oxygen (70 mL / min) to measure the oxidation onset temperature. During the test, 3 ± 5 mg of the sample was placed in an aluminum pan and heated from 20 °C to 380 °C at a constant heating rate of 10 °C / min in an oxygen stream of 70 mL / min. The extrapolated onset temperature of oxidation and the temperature of the maximum heat flow were determined from each DSC scan using the program STAR (TA Instruments). Oxidation tests were performed on the elastomer composition samples in order to compare their thermal stabilities by the oxidation onset temperature (OOT). The oxidation onset temperature was obtained under non-isothermal (dynamic) conditions from the intersection of the extrapolated baseline and the tangent of the exothermic peak using thermal analysis software (STAR). All experiments were performed in duplicate. Similar conditions were used for the isothermal oxidation tests.

[0173] The ozone dynamic test was carried out according to ISO 1431-1 and was determined at 50 °C for 70 h using air containing 50 pphm ozone with a 20% stress at 0.5 Hz. The specimens were visually inspected for cracks.

[0174] Tensile measurements were performed on samples of the elastomer composition vulcanized at 175 °C for 20 minutes according to the standard ISO 37:2005. In particular, the loads were measured at different elongation levels (50%, 100% and 300%) in the order of σ 50 、σ 100 、σ 300 , and the breaking stress and breaking elongation were in the order of σ B and ε B . The tensile tests were carried out on dumbbell-shaped specimens with a straight axis.

[0175] The dynamic mechanical properties were measured using an Instron dynamic device in tension-compression mode according to the following method. Specimens of the crosslinked elastomer composition having a cylindrical shape (length = 25 mm; diameter = 12 mm) and maintained at a predetermined temperature (10 °C, 23 °C and 70 °C) throughout the test duration were compression-preloaded to a 25% longitudinal deformation relative to the initial length and then subjected to a dynamic sinusoidal strain with an amplitude of ±3.5% relative to the length under preloading at a frequency of 100 Hz. The dynamic-mechanical properties were expressed as dynamic storage modulus (E') and loss factor (Tanδ) values. The tanδ value was calculated as the ratio between the loss (E") modulus and the storage (E') modulus.

[0176] The measured static and dynamic mechanical properties are summarized in Table 1 below.

[0177] Table 1

[0178]

[0179]

[0180] Synthesis of pyranone derivatives

[0181] Example 1. Synthesis of 3,4,5-triacetoxy-6-oxo-tetrahydro-pyran-2-carboxylic acid (1) (precursor)

[0182]

[0183] Charge 10 g of mucic acid (0.049 mol) and 51 mL of acetic anhydride (0.54 mol) into a 100-mL flask equipped with a magnetic stirrer and a condenser. Stir the mixture overnight at 130 °C. Isolate the pure product by filtration (yield 99%).

[0184] The product was characterized by NMR spectra and 1 The 1H NMR spectrum is shown in Figure 1 (400 MHz, DMSO-d6, δ, in ppm): 2.08 (s, 3H); 2.15 (s, 6H); 5.01 (dd, 1H); 5.27 (d, 1H); 5.51 (t, 1H); 5.89 (d, 1H); 12.10 (s, 1H).

[0185] Example 2. Synthesis of 3-hydroxy-2-oxo-2H-pyran-6-carboxylic acid (Compound 2)

[0186]

[0187] Add 1 g of CH3COONa·3H2O (0.049 mol) and the reaction mixture obtained in Example 1 to a 100-mL flask equipped with a magnetic stirrer and a condenser. Then stir the new reaction mixture at 100 °C for 12 hours. At the end of this time, add HCl solution (0.0002 mol, 2 ml, 36%). A white precipitate (59.8 g) forms a few minutes after addition. Once formed, remove the precipitate by filtration. On the other hand, concentrate the solution under reduced pressure until about 32 g of solution is obtained. Let the solution thus obtained stand until a new precipitate forms. After 1 day, repeat the process and isolate another 3.2 g of solid. Characterize the solid product obtained by 3 filtrations by NMR spectra (yield: 65%).

[0188] 1 The 1H NMR spectrum is shown in Figure 2 (400 MHz, DMSO-d6, δ, in ppm): 2.27 (s, 3H); 7.13 (d, 1H); 7.47 (d, 1H); 12.10 (s, 1H).

[0189] Synthesis of Ethyl 3-Hydroxy-2-oxo-2H-pyran-6-carboxylate (Compound 3), Example 3

[0190]

[0191] To a 100 ml flask equipped with a magnetic stirrer and a condenser, the product obtained in Example 2 (Compound (2)) (3.1 g), ethanol (30 ml) and 6 drops of sulfuric acid (1.0 g, 0.049 mol) were added. The mixture thus obtained was stirred overnight at 85 °C. At the end of said time, the reaction mixture was poured into a separatory funnel and water (180 mL) was added, and the pH was neutralized by adding a small amount of sodium bicarbonate. The mixture was extracted 3 times with dichloromethane (60 ml). The residual water was adjusted to alkaline pH with sodium bicarbonate. The organic phase was dried over sodium sulfate, then filtered and dried thoroughly under reduced pressure (yield: 99%).

[0192] The product was characterized by 1 1H NMR spectrum, and the spectrum is shown in Figure 3 (400 MHz, CDCl3-d6, δ, in ppm): 1.40 (t, 3H); 4.40 (q, 2H); 6.78 (d, 1H); 7.20 (d, 1H); 13C NMR (100 MHz, CDCl3): δ 14.17, 62.17, 112.93, 113.00, 140.85, 145.70, 159.14, 159.59 ppm).

[0193] Examples 4 - 8: Partial Replacement of Silica in Elastomer Compositions

[0194] According to the qualitative - quantitative compositions summarized in Table 2, elastomer compositions 4 - 8 were prepared via melt blending. Reference composition 4^ contains silica as the main reinforcing filler, together with carbon black; in compositions 5 - 7, silica has been partially replaced by the compounds according to the invention and an additional amount of carbon black, while in reference composition 8^, the same replacement was carried out using adipic acid (a saturated analogue of muconic acid).

[0195] Table 2

[0196] Ex.4^ Ex.5 Ex.6 Ex.7 Ex.8^ [phr] [phr] [phr] [phr] [phr] NR(SIR-20) 70 70 70 70 70 BR 30 30 30 30 30 CB N326 30 30 30 30 30 SILICA 35 12 12 12 12 X50S 5.6 5.6 5.6 5.6 5.6 ZnO 4 4 4 4 4 Stearic acid 2 2 2 2 2 6PPD 2 2 2 2 2 TBBS 1.8 1.8 1.8 1.8 1.8 Sulfur 2 2 2 2 2 CB N326 0 18.73 18.73 18.73 18.73 Compound (2) 0 0.99 0 0 0 Compound (3) 0 0 0.99 0 0 Mucic acid 0 0 0 0.99 0 Adipic acid 0 0 0 0 0.99

[0197] ^ indicates comparison.

[0198] Example 4 - Elastomer Composition Containing Silica and CB (Comparative Example)

[0199] 70 phr of natural rubber (SIR - 20) and 30 phr of poly(1,4 - butadiene) (BR) were fed into Plasticate in a Banbury mixer at 130 °C for 1 minute. Add CB, silica Zeosil 1156MP, and X50S to a mixer and mix at the same temperature for 3 minutes. Then add ZnO, stearic acid, and 6PPD and mix for 2 minutes.

[0200] Discharge the compound thus obtained at 130 °C.

[0201] Feed these composites again into the Banbury mixer at 45 °C. Then add sulfur and TBBS (N-tert-butyl-2-benzothiazolesulfenamide) and mix for another 2 minutes.

[0202] Discharge the final rubber compound and cool it at room temperature, and before characterization, mix it several times in a two-roll mill.

[0203] Example 5 - Elastomeric composition containing silica, CB, and compound 2

[0204] Repeat the procedure disclosed in Example 4, but 66% of the silica is replaced by the original CB and 0.99 phr of compound (2) obtained as disclosed in Example 2. Keep the same volume % of the filler.

[0205] Example 6 - Elastomeric composition containing silica, CB, and compound 3

[0206] Repeat the procedure disclosed in Example 4, but 66% of the silica is replaced by the original CB and 0.99 phr of compound (3) obtained as disclosed in Example 3. Keep the same volume % of the filler.

[0207] Example 7 - Elastomeric composition containing silica, CB, and muconic acid

[0208] Repeat the procedure disclosed in Example 4, but 66% of the silica is replaced by the original CB and 0.99 phr of muconic acid. Keep the same volume % of the filler.

[0209] Example 8 - Elastomeric composition containing silica, CB, and adipic acid (comparative example)

[0210] Repeat the procedure disclosed in Example 4, but 66% of the silica is replaced by the original CB and 0.99 phr of adipic acid. Keep the same volume % of the filler.

[0211] Elastomeric compositions 4 - 8 by dynamic mechanical characterization of axial stress

[0212] In Table 3, the data obtained from the dynamic mechanical tests by applying a sinusoidal axial stress are shown. The experimental conditions for the tests are as described above.

[0213] Table 3

[0214] Ex.4^ Ex.5 Ex.6 Ex.7 Ex.8^ E’@10℃ 3.88 3.74 3.84 3.81 3.91 E”@10℃ 0.66 0.68 0.70 0.68 0.78 Tanδ@10℃ 0.170 0.181 0.181 0.178 0.200 E’@23℃ 3.69 3.51 3.60 3.57 3.47 E”@23℃ 0.55 0.57 0.59 0.57 0.64 Tanδ@23℃ 0.149 0.163 0.163 0.160 0.184 E’@70℃ 3.32 3.16 3.24 3.22 2.95 E”@70℃ 0.46 0.50 0.51 0.50 0.60 Tanδ@70℃ 0.139 0.159 0.158 0.155 0.203 <![CDATA[ΔE’(E’ 10℃ -E’ 70℃ )]]> 0.56 0.58 0.60 0.59 0.96

[0215] ^ indicates comparison.

[0216] Using the compounds according to the invention (compounds 2, 3 and muconic acid, Examples 5, 6 and 7 respectively) as components of the elastomeric composition allows partial replacement of silica with CB and substantially reproduces the same dynamic-mechanical properties measured for the reference composition (Ex.4^). This behavior was not observed for mixtures with adipic acid that do not contain an unsaturated group or -OH group in the alpha position of the carbonyl.

[0217] In addition to this general comment, it is important to observe that:

[0218] (i) The value of the storage modulus E' of the elastomeric compositions of the invention (Ex.5 - 7) at low temperature is slightly lower than that of the reference composition (Ex.4^). This means that the composition has lower rigidity at low temperature, which is certainly an advantage;

[0219] (ii) The ΔE′ value (E′10°C - E′70°C) of the compositions of the invention (Ex.5 - 7) is substantially the same (slightly higher) as that of the reference composition (Ex.4^). This means that, although silica is partially replaced by CB, the compositions of the invention have substantially the same dynamic rigidity stability as the reference composition with increasing temperature;

[0220] (iii) The composition containing adipic acid (Ex.8^) shows a slightly higher E′ value at low temperature, and the ΔE′ value (E′10°C - E′70°C) is much greater than that of the reference composition (Ex.4^) and the compositions of the invention (Ex.5 - 7).

[0221] (iv) The tanδ values of the compositions of the invention (Ex.5 - 7) are substantially the same at all temperatures relative to the reference composition (Ex.4^), while for the composition containing adipic acid (Ex.8^), they are significantly higher. It is well known that for rubber compositions used in tire treads, it is beneficial to have higher hysteresis at low temperature and lower tanδ at high temperature. On the contrary, for elastomeric composites used in other tire compositions, it is beneficial to have low hysteresis at each temperature.

[0222] Characterize the elastomeric compositions 4 - 8 using tensile tests

[0223] The tensile properties are determined by the quasistatic measurement disclosed above. In Table 4, the data obtained from the tensile tests are shown.

[0224] Table 4

[0225] Ex.4^ Ex.5 Ex.6 Ex.7 Ex.8^ <![CDATA[σ 50 (Mpa)]]> 0.76 0.77 0.74 0.81 0.60 <![CDATA[σ 100 (MPa)]]> 1.08 1.09 1.03 1.18 0.78 <![CDATA[σ 300 (MPa)]]> 4.09 4.05 3.68 4.60 2.02 <![CDATA[σ B (MPa)]]> 22.36 23.92 21.38 19.90 9.43 <![CDATA[ε B (%)]]> 692.01 749.08 713.94 653.98 667.22 <![CDATA[Energy J / cm 3 > 52.80 62.78 52.06 46.39 22.87

[0226] ^ indicates comparison.

[0227] The tensile properties confirmed the commented data from the dynamic-mechanical characterization that have been reported.

[0228] In fact, the elastomeric compositions of the present invention (Ex. 5 - 7) have tensile properties consistent with those of the reference composition (Ex. 4^). In particular, it is noteworthy that the composition containing Compound 3 (Ex. 7) has better overall ultimate properties.

[0229] Conversely, the composition containing adipic acid (Ex. 8^) shows significantly different tensile property values: much lower stress values at all elongation rates and much poorer overall ultimate properties. It appears that adipic acid does not promote the reinforcement of the elastomeric composite.

[0230] Examples 9 - 16: The compounds of the present invention as antioxidants and antiozonants in elastomeric compositions

[0231] According to the qualitative - quantitative compositions summarized in Table 5 below, elastomeric compositions 9 - 16 were prepared via melt blending.

[0232] Briefly, 50 phr of isoprene rubber (IR) and 50 phr of poly(1,4 - butadiene) (BR) were fed into an internal mixer and kneaded at 110 °C for 1 minute. CB was added to the mixer and mixed at the same temperature for 3 minutes. Then ZnO, stearic acid, wax, resin, and a selective protective agent (one or more) (TMQ, 6PPD, or Compound 3) were added and mixed for 2 minutes. The compounded mixture thus obtained was discharged at 110 °C.

[0233] These composites were fed again into the internal mixer at 80 °C, then sulfur and TBBS (N - tert - butyl - 2 - benzothiazolesulfenamide) were added, and mixed for another 2 minutes. The final rubber composite was discharged and cooled at room temperature, and before characterization, it was mixed several times in a two - roll mill.

[0234] Table 5

[0235]

[0236]

[0237] ^ indicates comparison.

[0238] The above elastomeric compositions 9 - 16 all contain carbon black (CB N550) as a filler. The reference composition 9^ does not contain any antioxidant / antiozonant system; the reference compositions 10^ and 12^ contain only TMQ; the reference compositions 11^ and 13^ contain only 6PPD; the reference composition 14^ contains both TMQ and 6PPD. In the compositions according to the invention, the compounds according to the invention, in particular pyrone derivatives (Compound 3), are used together with 6PPD (Ex.15) or TMQ (Ex.16).

[0239] Evaluation of the oxidation onset temperature (OOT) based on DSC analysis

[0240] The OOT tests were performed on the elastomeric compositions 9 - 16 disclosed above. The data are summarized in Table 6.

[0241] Table 6

[0242]

[0243]

[0244] ^ indicates comparison.

[0245] It appears that Compound 3 is a suitable antioxidant and anti - ozonant component in the elastomeric composition, especially when it is used to replace only one of the two oil - based substances, which means replacing 6PPD (Ex.16) or replacing TMQ (Ex.15).

[0246] By comparing Ex.14^ and Ex.15, it can be seen that the same values of OOT 1 and OOT 2 are obtained. In fact, replacing TMQ with Compound 3 produces values that are essentially consistent with the reference compound. Higher values are recorded from the integration of the exothermic peak.

[0247] On the other hand, by comparing Ex.14^ and Ex.16, it can be seen that replacing 6PPD with Compound 3 results in a significant decrease in the OOT value.

[0248] Evaluation of thermal stability based on thermogravimetric analysis

[0249] Two elastomeric compositions that showed the most satisfactory results in the previous tests via TGA analysis, namely the compositions of Ex.15 - 16, were compared with the reference composition 9^ that does not contain an antioxidant / antiozonant system and the reference composition 14^ that contains both TMQ and 6PPD. The data from the TGA analysis are summarized in Table 7.

[0250] Table 7

[0251] Example T<300℃ T>300℃ Final residue %@45min 9^ ND 40.0 59％ 67％ 14^ 3.77 34.8 61％ 70.5％ 15 5.28 31.0 63.58％ 71％ 16 3.79 30.1 66％ 73％

[0252] ^ indicates comparison.

[0253] TGA analysis showed that replacing 6PPD or TMQ with the pyranone derivative (i.e., compound 3) led to greater thermal stability compared to the reference composition (14^), as indicated by the amount of residue mass.

[0254] Vulcanization of elastomeric compositions 14 - 16

[0255] The elastomeric compositions of Ex. 15 - 16 and the reference composition 14^ were vulcanized at 170 °C for 10 minutes. The measured vulcanization properties are summarized in Table 8 below, where the cure rate is defined by the following formula:

[0256] Cure rate = M H - M L / t 90 - t S1

[0257] Table 8

[0258]

[0259] ^ indicates comparison.

[0260] Replacing TMQ or 6PPD with the pyranone derivative (i.e., compound 3) led to an increase in ML, which is an index of the viscosity of the composition. In addition, the presence of the pyranone derivative did not affect the scorch time of vulcanization, as revealed by t S1 .

[0261] Tensile properties of elastomeric compositions 14 - 16

[0262] Tensile properties were determined by quasi-static measurements. The data are in Table 9.

[0263] Table 9

[0264]

[0265]

[0266] ^ indicates comparison.

[0267] The tensile properties of the elastomeric composition (Ex. 15) obtained by replacing TMQ with the pyranone derivative appeared to be essentially consistent with those of the reference composition (Ex. 14^), with better elongation at break and energy at break. Replacing 6PPD with the pyranone derivative (Ex. 16) did not significantly affect the tensile properties: the stress was in good agreement, and the value of the overall ultimate property was slightly lower in terms of the stress at break, but the higher elongation rate led to a higher energy at break relative to the reference composition (Ex. 14^) anyway.

[0268] The elastomeric composition was aged at 70 °C for 2 weeks and the tensile properties were measured again. This experiment is particularly significant as it gives an indication of the ability of the compound used as antioxidant / antiozonant to protect the elastomeric composition. The data was summarized in Table 10 by reporting the percentage change of each value when compared to the value measured before aging.

[0269] Table 10

[0270] Ex.14^ Ex.15 Ex.16 <![CDATA[σ 50 (Mpa)]]> 10％ 16％ 11％ <![CDATA[σ 100 (MPa)]]> 14％ 21％ 17％ <![CDATA[σ 300 (MPa)]]> 9％ 17％ 18％ <![CDATA[σ B (MPa)]]> -19％ -15％ -11％ <![CDATA[ε B (%)]]> -21％ -20％ -18％ <![CDATA[Energy J / cm 3 > -36％ -28％ -26％

[0271] ^ indicates comparison.

[0272] Very similar results were obtained, thus confirming that the pyrone derivative is a suitable chemical compound for protecting the elastomeric composition against the action of oxygen and ozone. In particular, when the pyrone derivative is present, the ultimate properties are less affected by aging. In particular, aging has a lower impact on the composite material of Example 16 across all test parameters.

[0273] Evaluation of Antiozonant Activity

[0274] The elastomeric composition of Ex. 16 containing TMQ and Compound 3 was analyzed via the dynamic ozone test as described above and compared with the reference composition 9^ without an antioxidant / antiozonant system and the reference composition 14^ containing both TMQ and 6PPD.

[0275] The data from the ozone test was summarized in Table 11.

[0276] Table 11

[0277] Ex.9^ Ex.14^ Ex.16 Ozone dynamic test 50C 70h 4 0 0,5

[0278] ^ indicates comparison.

[0279] The samples were visually inspected before and after ozone aging. The evaluation of the samples was indicated by a number in the range from 0 (best evaluation) to 4 (worst evaluation, the sample was destroyed due to ozone aging).

[0280] Here it can be seen how the samples of Ex. 14^ and Ex. 16 are much better than the compound of Ex. 9^ without a protecting agent.

[0281] Very similar results were obtained with the two samples of Ex. 14^ and Ex. 16, confirming that the pyrone derivative is a suitable chemical compound for protecting the elastomeric composition against ozone.

Claims

1. A process for preparing an elastomeric composition, said elastomeric composition comprising a compound represented by the following formula (I): wherein the compound of formula (I) can be linear or cyclic, and when the compound is a linear compound, the symbol (C) does not represent a bond, and when the compound is a cyclic compound, the symbol (C) represents a bond; m, v, p, q, r, u and n can independently be equal to 1 or equal to 0; and X1 and Y can be O or NR7; and wherein: R7 is selected from: hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, and heteroaryl; and if X1 and Y are NR7, then: - R1, R6 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, and heteroaryl; if X1 and Y are O, then: - R1, R6 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, heteroaryl, alkali metal, alkaline earth metal and transition metal, or wherein R8, R9, R 10 , R 11 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, and heteroaryl; and wherein: R2, R3, R4, R5 are independently selected from: hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl or alkynyl, aryl, linear or branched C1-C6 alkylaryl, linear or branched C2-C6 alkenylaryl, linear or branched C2-C6 alkynyl-aryl, and heteroaryl; and wherein: - when the compound of formula (I) is a linear compound: n is 1 and v and / or m is 1; the symbols (A) and (B) independently represent a single bond or a double bond, and if the symbol (A) is a double bond, then p and v are 0 and m is 1, or p and m are 0 and v is 1; if the symbol (B) is a double bond, then q and r are 0 and u is 1, or q and u are 0 and r is 1; if the symbol (A) is a single bond, then p, v and m are 1; if the symbol (B) is a single bond, then q, r and u are 1; and - when the compound of formula (I) is a cyclic compound: the symbols (A) and (B) are double bonds, m, v, p, q, n and u are 0 and r is 1, or m, v, p, q, n and r are 0 and u is 1; the method comprises the following steps: a) providing one or more elastomers, a compound of formula (I) and at least one reinforcing filler; and b) performing at least one mixing step.

2. The method according to claim 1, wherein the compound of formula (I) is a compound represented by formula (II): wherein n is 1; and wherein the symbols (A) and (B) independently represent a single bond or a double bond, and if the symbol (A) is a double bond, then p and v are 0 and m is 1, or p and m are 0 and v is 1; If the symbol (B) is a double bond, then q and r are 0 and u is 1, or q and u are 0 and r is 1; If the symbol (A) is a single bond, then p, v, and m are 1; If the symbol (B) is a single bond, then q, r, and u are 1; and wherein X1, Y, and R1-R6, when present, are as defined in claim 1.

3. The method according to claim 1, wherein the compound of formula (I) is a compound represented by formula (VIII): wherein Y, X1, R1, and R5 are as defined in claim 1.

4. The method according to any one of claims 1-3, wherein R1 and R6 are independently selected from: hydrogen, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, and aryl.

5. The method according to any one of claims 1-4, wherein R2-R5 are independently selected from: hydrogen, C2-C6 acyl, C1-C6 alkyl, linear or branched C2-C6 alkenyl, and aryl.

6. The method according to any one of claims 1-5, wherein the compound of formula (I) is provided in an amount of at least 0.1 phr.

7. The method according to any one of claims 1-6, wherein at least one of the one or more elastomers is an unsaturated elastomer selected from the group consisting of: poly(1,4-cis-isoprene), natural rubber or synthetic polymers, poly(3,4-isoprene), poly(butadiene), poly(butadiene) having a high content of 1,4-cis units, isoprene / isobutene copolymer, halogenated isoprene / isobutene copolymer, halogenated butyl rubber, chlorinated butyl rubber, brominated butyl rubber, 1,3-butadiene / acrylonitrile copolymer, styrene / 1,3-butadiene copolymer, styrene / isoprene / 1,3-butadiene copolymer, and styrene / 1,3-butadiene / acrylonitrile copolymer and mixtures thereof.

8. The method according to any one of claims 1-7, wherein the at least one reinforcing filler is selected from the group consisting of: sp 2 hybrid carbon allotropes, silica, layered silicates, mixed oxides of aluminum and magnesium having a layered structure, alumina, and aluminosilicates, and mixtures thereof.

9. The method according to claim 8, wherein said sp 2 hybridized carbon allotropes are selected from the group consisting of carbon black, graphene, bilayer graphene, 3 to 10 layer graphene, graphite, high surface area graphite, single-walled or multi-walled carbon nanotubes, longitudinally or helically extended carbon nanotubes, nanocones, nanohorns, nanorings, fullerenes, and mixtures thereof.

10. The method according to claim 9, wherein the sp 2 hybridized carbon allotropes are selected from the group consisting of carbon black, graphene, graphite, high surface area graphite, single-walled or multi-walled carbon nanotubes, and mixtures thereof.

11. A method according to any one of claims 1 - 10, wherein the at least one reinforcing filler is a hybrid carbon allotropes provided in an amount of at least 1 phr 2 Hybrid carbon allotropes 12. The method according to any one of claims 9 - 11, wherein said sp 2 hybridized carbon allotropes are carbon black.

13. The method according to claim 12, wherein the carbon black is provided in an amount of at least 10 phr.

14. The method according to any one of claims 1-10, wherein the at least one reinforcing filler is a mixture of carbon black and silica.

15. The method according to claim 14, wherein the carbon black is provided in an amount of at least 10 phr, and the silica is provided in an amount equal to or less than 100 phr.

16. The method according to any one of claims 9-15, wherein the at least one reinforcing filler is provided in an amount of 10 phr to 150 phr.

17. The method according to any one of claims 1-16, wherein in step a), one or more additives are further provided, the additives being selected from the group consisting of: anti-aging agents, plasticizers, binders, modified resins, coupling agents, and mixtures thereof.

18. The method according to claim 17, wherein the anti-aging agents are selected from antioxidants, antiozonants, and mixtures thereof.

19. The method according to claim 18, wherein at least one antioxidant or at least one antiozonant is provided in the step a).

20. The method according to claims 18 - 19, wherein each of the at least one antioxidant and / or at least one antiozonant is independently provided in an amount of 0.1 phr to 20 phr.

21. The method according to any one of claims 1 - 20, wherein one or more vulcanizing agents are further provided, which optionally comprise activators and / or accelerators.

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