Elastomeric compositions for tires, elastomeric compounds and tires comprising them comprising a new crosslinking functionalizing agent

Abstract

This invention relates to compositions for elastomeric tire compounds, comprising a specific crosslinking functionalizing agent containing at least one tetrazolium functional group and at least one carbene or azibene precursor, characterized by precise temperatures for activating these two functional groups, vehicle tire components comprising them, and wheel tires. Advantageously, the crosslinking functionalizing agent of this invention allows, on the one hand, in-situ functionalization of commonly available polymers under mild conditions, and on the other hand, crosslinks the compound, thereby improving its fracture properties and reducing its hysteresis.

Description

[0001] This invention relates to elastomer compositions and compounds for tires, containing novel crosslinking functionalized agents characterized by multiple activation temperatures, and corresponding tire components and vehicle wheel tires comprising them. Existing technology

[0002] In the rubber industry, and more specifically in the tire industry, various functionalized polymers are known to be used, often blended with non-functionalized polymers such as natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR), etc., to improve some properties of the material after vulcanization.

[0003] Typically, in tires, functionalized polymers are used for various purposes, such as improving uniformity or increasing the degree of crosslinking of sulfur-cured materials (crosslinked functionalized polymers), making the distribution of reinforcing fillers more uniform, increasing the compatibility of dissimilar polymers used in blends, and more generally, enhancing the mechanical properties of materials and increasing their durability and / or reducing their rolling resistance and thus reducing vehicle wear.

[0004] For example, in order to improve the interaction between the polymer phase and silica, and thus reduce the rolling resistance of the tread, functionalized polymers with polar groups—such as those described in patent US8816014 representing Asahi or patent US9434792 representing JSR—are used. These groups, by interacting with silica, will increase its dispersibility in the elastomer material.

[0005] However, the preparation of functionalized polymers is currently complex, cost-inefficient, and almost uncommon.

[0006] In fact, typically, in order to prepare functionalized polymers containing specific functionalities and certain proportions, their overall specific synthesis is carried out by copolymerization of target precursors under strictly controlled, expensive and highly specialized conditions, in which these functionalities are introduced upstream by specialized methods and reactors.

[0007] Instead, a more general preparation method is preferred, which introduces specific functionality not in the formed polymer but on its pre-formed backbone, downstream of the polymerization process, i.e., directly onto the end polymer through end functionalization or grafting. Ideally, a technically simple preparation is required, using common equipment and less stringent conditions compared to those required for classical (co)polymerization in solution or emulsion. Invention Overview

[0009] The applicant has conducted research to prepare cross-linked functionalized polymers that are suitable for improving one or more of the aforementioned properties of elastomer materials for tires by overcoming the shortcomings in the preparation of currently used functionalized polymers.

[0010] In this regard, the applicant has set the aim of making the preparation of certain cross-linked functionalized polymers universal, not only by transferring functionalization downstream of polymerization, thus allowing easy diversification of products starting from commercially available, inexpensive and readily available non-functionalized polymers, but also by extending the applicability of functionalization reactions to low-reactivity polymers.

[0011] Furthermore, the applicant expects to be able to functionalize polymers using a common mixer and under simple conditions during conventional elastomer processing steps, without incurring material processing difficulties by thickening through early crosslinking and then ideally crosslinking the functionalized polymer directly in the mold during the final vulcanization step for the compound.

[0012] Finally, the applicant expects the functionalized polymers of this study, when crosslinked in rubber compounds, to impart improved mechanical properties and optionally lower heat dissipation, and to offer advantages for tire applications such as longer service life and lower consumption.

[0013] The applicant achieved the above objectives by focusing on novel crosslinking functionalizing agents characterized by bifunctionalization, namely, containing a carbene or azibene precursor group and at least one 2,5-disubstituted tetrazolium. The very different reactivity and activation temperatures of the two functionalizations allow for a clear separation of the polymer backbone functionalization step in the compound from the subsequent crosslinking step. Specifically, a preliminary, even low-reactivity, polymer functionalization step is achieved through simple mixing under very mild conditions, such as at a temperature of about 120-140°C, thereby maintaining the high processability of the elastomer material, followed by the final curing step in a mold at temperatures typically above 140°C to allow for the crosslinking of the tetrazolium functional groups and the vulcanizing agent.

[0014] To the applicant's knowledge, the different functionalities of the crosslinking functionalizing agents of the present invention are not typically used together, just as they are not used in the tire materials industry.

[0015] Regarding the reactivity of the tetrazolium functional group, it is known from the literature, for example from J.K. Stille, A.T. Chen, Macromolecules, 378, 5, (1972), that upon heating or irradiation with ultraviolet light, 2,5-disubstituted tetrazolium decomposes with the development of nitrogen, producing a highly reactive intermediate (nitrile imine) capable of reacting with activated double bonds (A=B), such as vinyl groups, as shown in Scheme 1 below:

[0016] Option 1

[0017]

[0018] This 1,3-dipolar cycloaddition reaction leads to the formation of stable and easily identifiable substituted pyrazolines, as they are fluorescent upon exposure to ultraviolet radiation. The reaction does not occur with tetrazolium that is disubstituted or monosubstituted at other positions.

[0019] The temperature at which 2,5-disubstituted tetrazolium decomposes, also referred to herein as the activation temperature T-Tetr of the tetrazolium, depends on the nature of the groups present at the 2,5 positions of the tetrazolium, as discussed in Table 1 of J. Appl. Polym. Science, Vol. 28, pp. 3671-3679 (1983), in Table 2 of Macromolecules, Vol. 5, No. 4, (1972), pp. 377-384, and as investigated by the applicant in this experimental section (Tables 1 and 2).

[0020] Patent application WO201137143A1, representing the applicant, describes polytetraazole agents for tire compounds that can be anchored to activated double bonds of common elastomeric polymers, such as vinyl groups, by functionalization. The experimental portion of WO2021137143A1 describes crosslinking functionalizing agents in which the tetraazoles are equal in quantity and have an activation temperature of not less than 170°C.

[0021] In the carbene precursor group, Lepage et al.’s article, Science 366, 875-878 (2019), describes bisacrylidine, particularly di-bisacrylidine, as a crosslinking agent for low-reactive polyolefin polymers.

[0022] The article J.Mech.Behav.Biomed.Materials101(2020)103405 describes ternary adhesive blends based on the reactivity of bisacrylidine.

[0023] The article Macromolecules (2008), 41, 9284-9289, reported the formation of a network by copolymerizing sulfonyl azide and nitrobenzene precursors incorporated into a polymer through thermal activation.

[0024] Patent application WO2017011533A1 describes possible uses of stable carbides that cannot be adapted to CH or CC bonds, for example, within nucleophiles, to polymerize elemental sulfur in polymer materials.

[0025] In their research, the applicant discovered that, in addition to the many methodological advantages discussed above, the crosslinking functionalizing agents of the present invention impart improved properties to the final adhesives incorporated therein, as further explained below.

[0026] Therefore, the first aspect of the present invention is a crosslinking functionalizing agent of formula (I) for elastomeric compounds:

[0027]

[0028] in

[0029] n is an integer from 1 to 3;

[0030] B is an organic group capable of producing carbene or nitrobenes.

[0031] A represents at least a divalent organic linker residue between the B group and the one or more tetrazolium groups, wherein A is covalently linked to the 2 or 5 position of the one or more tetrazolium groups, wherein the one or more tetrazolium groups are 2,5-disubstituted tetrazolium groups;

[0032] R is an organic group covalently attached to the 5- or 2-position of one or more tetrazoles, selected from straight-chain or branched C1-C2 groups. 10 Alkyl; C6-C 20 Aryl; C3-C 10 Cycloalkyl; a 5- or 6-membered saturated, unsaturated, or aromatic monocyclic or bicyclic fused heterocyclic group containing at least one heteroatom selected from N, S, and O, wherein R is optionally substituted with at least one electron-withdrawing group EW or at least one electron-donating group ED.

[0033] The cross-linking functionalization of the formula (I) is characterized by the activation temperature (TB) of group B and one or more activation temperatures (T-Tetr) of the one or more tetrazolium, wherein the one or more activation temperatures (T-Tetr) are higher than the activation temperature (TB).

[0034] Another aspect of the present invention is a functionalized diene elastomer polymer obtained by reacting a diene elastomer polymer with at least one reagent of formula (I) as defined above.

[0035] Another aspect of the present invention is a method for preparing a functionalized diene elastomer polymer, comprising:

[0036] -Provides diene elastomer polymers;

[0037] - Provide reagents of formula (I) as defined above,

[0038] - The diene elastomer polymer and the reagent of formula (I) are mixed, and the blend is held at a temperature T1 that is higher than the activation temperature (TB) of the reagent of formula (I) and lower than the one or more activation temperatures (T-Tetr) for a time sufficient to complete the functionalization reaction of the diene elastomer polymer to obtain a functionalized diene elastomer polymer.

[0039] Another aspect of the present invention is an elastomer composition for tire rubber compounds, comprising at least:

[0040] At least one diene elastomer polymer with a phr of -100 phr

[0041] -At least one reinforcing filler with a minimum of 1 phr,

[0042] - At least 0.1 phr of at least one reagent of formula (I) as defined above, and

[0043] -0 to 20 phr vulcanizing agent.

[0044] Another aspect of the invention is an elastomeric compound for tires obtained by mixing and possibly vulcanizing the elastomeric composition according to the invention.

[0045] Another aspect of the present invention is a method for preparing an elastomer tire compound that is vulcanized and optionally crosslinked according to the present invention, comprising:

[0046] -(i) The step of mixing the following substances in one or more stages:

[0047] At least one diene elastomer polymer with a phr of -100 phr

[0048] - At least 0.1 phr of at least one reagent of formula (I) as defined above, and optional other components other than the vulcanizing agent, maintaining the temperature at a value T1 that is always below one or more activation temperatures (T-Tetr) of the tetrazolium component of the reagent of formula (I), and at least for one mixing step, above the activation temperature (TB) of group B in the same reagent of formula (I), to obtain a crosslinkable non-vulcanizable compound comprising a functionalized diene elastomer polymer (non-productive step).

[0049] -(ii) The step of adding the vulcanizing agent and optionally other components from the vulcanizing package to the aforementioned rubber compound and mixing at a temperature T2 always below both the temperature (T-Tetr) for activating the tetrazolium component and the vulcanization temperature (TV) of the rubber compound to obtain a vulcanizable and crosslinkable rubber compound (production step); and

[0050] -(iii) The step of curing and optionally crosslinking the aforementioned rubber compound by heating, preferably in a mold, at a temperature T3 above the vulcanization temperature (TV) of the rubber compound, and optionally at one or more of the aforementioned temperatures for activating the tetrazolium component (T-Tetr), to obtain the vulcanized and optionally crosslinked elastomer compound according to the invention.

[0051] Another aspect of the present invention is a vehicle wheel tire component comprising an elastomeric compound according to the present invention, or preferably composed of an elastomeric compound according to the present invention.

[0052] Another aspect of the invention is a vehicle wheel tire that includes at least one tire component according to the invention.

[0053] Advantageously, the reagent of formula (I) of the present invention improves the properties of elastomeric tire compounds when incorporated and vulcanized, even in the case of polymer blends with poor compatibility.

[0054] By changing the type of substituents on the tetrazolium ring and on group B, the tetrazolium ring (T-Tetr) and group B carbene or azibene precursor (TB) of the reagent of formula (I) can be appropriately adjusted, and the advantages of the method and product that would otherwise not be available can be obtained, as shown below.

[0055] definition

[0056] The term "crosslinking functionalizing agent" is used to refer to compounds containing a B-group carbene or niobene precursor that produces a carbene or niobene at temperatures (TB) typically between 110 and 140 °C. Under mild conditions, such as by adaptation to covalent bonds like CH, CC, etc., the carbene or niobene reacts nonselectively with functional groups or diene elastomer polymer bonds, thereby functionalizing even poorly reactive polymers.

[0057] Furthermore, the crosslinking functionalizing agent contains at least one 2,5-disubstituted tetrazolium, i.e., at least one tetrazolium capable of decomposing and releasing nitrogen gas at a precise temperature (T-Tetr) above (TB) and typically above 140°C, forming a reactive nitrile imine intermediate that leads to crosslinking through selective reaction with activated double bonds of the polymer, such as vinyl groups. The remaining structure of the crosslinking functionalizing agent, i.e., the remaining structure other than the specific reactive activatable functional group B and the 2,5-disubstituted tetrazolium, such as the linker A or substituent R, is stable upon undergoing sulfidation.

[0058] The term "electron-donating group ED" is used to indicate an atom or group of atoms that contributes to increasing the electron density on adjacent atoms, such as the groups -CH3, -OH, -O-alkyl, and -NH2.

[0059] The term “electron-withdrawing group (EW)” is used to refer to an atom or group of atoms that helps to reduce the electron density on adjacent atoms, such as -NO2, -CN, -COOH, and halogens.

[0060] The expression "organic group capable of generating carbene or nitrobenes" or "carbene or nitrobene precursor group" (group B) indicates a functional group that, through thermal or photo-stress decomposition, releases small molecules, typically nitrogen or carbon monoxide, and forms highly reactive substances such as carbene or nitrobenes. In the case of thermal activation, the temperature at which the reactive substance forms is denoted here as the activation temperature TB. The reactive substance can react not only with activated double bonds but also with less reactive bonds such as CH, OH, SH, NH, or CC.

[0061] The expression "activation temperature (T-Tetr) of the tetrazolium component" is used to indicate the temperature at which at least one 2,5-disubstituted tetrazolium begins to decompose, lose nitrogen, and form a nitrile imine intermediate. In the case of rubber compounds containing several different tetrazolium reagents of formula (I) or blends containing reagents of formula (I) (which contain different tetrazoliums), different activation temperatures of the tetrazolium component may occur in the system.

[0062] The term "activation temperature of group B (TB)" is used to indicate the temperature at which precursor group B begins to decompose and form carbene or nitrobenes.

[0063] The term "vulcanization temperature (TV)" is used to indicate the temperature at which a vulcanizable elastomer compound, including all components containing vulcanizing agents, begins to vulcanize, i.e., crosslinking, thereby typically forming (poly)sulfide bridges.

[0064] The expression "multiple activation temperatures" associated with the crosslinking functionalizing agent of the present invention is used to indicate that it can react in stages to different temperatures because it has at least two different functional groups, particularly at least one 2,5-disubstituted tetrazolium precursor of a nitrile imine and a B-carbene or azibene precursor, which can be thermally activated. Alternatively, these functional groups can also be activated by UV light.

[0065] The term "elastomer composition for tire compounds" is used to indicate a composition comprising at least one diene elastomer polymer and one or more additives, which, by mixing and optionally heating, provides an elastomer compound suitable for tires and their components.

[0066] The components of the elastomer composition are typically not introduced into the mixer simultaneously, but rather added sequentially. In particular, vulcanizing additives, such as vulcanizing agents and optionally accelerators and retarders, are typically added in a downstream step relative to the incorporation and processing of all other components.

[0067] In vulcanizable elastomer compounds, the individual components of the elastomer composition may be altered or no longer individually traceable, provided they are completely or partially modified due to interactions with other components, thermal and / or mechanical processing. The term "elastomer composition" herein is intended to include all components used in the preparation of the elastomer compound, regardless of whether they are actually present simultaneously, whether they are introduced sequentially, or whether they are subsequently traceable in the final elastomer compound or tire.

[0068] The term "elastomer compound" is used to refer to a blend that can be obtained by mixing at least one elastomer polymer with at least one additive commonly used in the preparation of tire compounds and optionally heating.

[0069] The term "non-vulcanizable elastomer compound" is used to refer to a blend that can be obtained by mixing at least one elastomer polymer with at least one additive (excluding vulcanizing agents) commonly used in the preparation of tire compounds and optionally heating.

[0070] The term "vulcanizable elastomer compound" is used to refer to a ready-to-use vulcanizable elastomer blend that can be obtained by incorporating all additives, including vulcanizing additives, into a non-vulcanizable elastomer blend.

[0071] The term "vulcanized elastomer compound" is used to refer to materials that can be obtained by vulcanizing vulcanizable elastomer compounds.

[0072] The terms "non-crosslinkable, crosslinkable, crosslinkable, etc." are used to indicate the crosslinking reaction of the functionalized diene elastomer polymer obtained by functionalizing the diene elastomer polymer with the reagent of formula (I), especially the reaction of the nitrile imine derived from the decomposition of the 2,5-disubstituted tetrazolium bound to the functionalized diene elastomer polymer with the double activated bonds of the polymer chain in the rubber compound.

[0073] In this document, the term "non-crosslinkable compound" is used to refer to a compound that does not contain a functionalized diene elastomer polymer, the term "crosslinkable compound" is used to refer to a compound that contains an unreacted functionalized diene elastomer polymer, and the term "crosslinked compound" is used to refer to a mixture that has been crosslinked by reacting the 2,5-disubstituted tetrazolium in the functional groups of the functionalized diene elastomer polymer with the activated double bonds of the elastomer polymer in the compound.

[0074] The term "green" is used to refer to materials, rubber compounds, compositions, parts, or tires that have not yet been vulcanized.

[0075] The term "vulcanization" is used to refer to, for example, the crosslinking reaction of natural or synthetic rubber induced by a sulfur-based vulcanizing agent.

[0076] The term "vulcanizing agent" is used to refer to compounds that can transform natural or synthetic rubber into elastic and resistant materials through three-dimensional cross-linking by forming intermolecular and intramolecular bonds.

[0077] The term "vulcanization accelerator" is used to refer to compounds that can reduce the duration and / or operating temperature of the vulcanization process, such as TBBS, general sulfenamides, thiazoles, dithiophosphates, dithiocarbamates, guanidines, and sulfur donors such as thiuram.

[0078] The term "vulcanization activator" is used to refer to compounds that can further promote vulcanization, enabling it to occur in a shorter time and optionally at a lower temperature. An example of an activator is the stearic acid-zinc oxide system.

[0079] The term "delayed vulcanization" is used to describe compounds that can delay the initiation of the vulcanization reaction and / or inhibit unwanted secondary reactions, such as N-(cyclohexylthio)phthalimide (CTP).

[0080] The term "vulcanizing package" is used to refer to a combination of a vulcanizing agent and one or more vulcanizing additives selected from vulcanizing activators, accelerators and retarders.

[0081] The term "elastomeric polymer" is used to refer to a natural or synthetic polymer that, after vulcanization, can be repeatedly stretched to at least twice its original length at room temperature and recovers substantially immediately and forcefully to its approximate original length after the tensile load is removed (as defined by the ASTM D1566-11 standard terminology related to rubber).

[0082] The term "diene elastomer polymer" is used to refer to an elastomer polymer derived from the polymerization of one or more monomers, at least one of which is a conjugated diene.

[0083] The term "reinforcing filler" or filler is used to refer to compounds that, when incorporated into elastomer compounds, can improve the static and dynamic mechanical properties of the vulcanized elastomer components.

[0084] The term "mixing step (I)" is used to refer to a step in a method for preparing an elastomer compound, wherein one or more additives, in addition to the vulcanizing agent provided in step (ii), may be incorporated by mixing and optionally heating. Mixing step (I) is also referred to as a "non-productive step." In the preparation of the compound, non-productive step (I) may include several mixing stages.

[0085] The term "mixing step (ii)" is used to indicate a subsequent step in the method of preparing an elastomer compound, wherein a vulcanizing agent and optionally other additives from the vulcanizing package are introduced into the elastomer compound obtained by step (I) and incorporated by mixing at a controlled temperature below the vulcanization temperature TV, typically at a mixing temperature below 120°C, to provide a vulcanizable elastomer compound. Mixing step (ii) is also referred to as a "production step" and may include several stages, although it typically consists of only one stage.

[0086] For the purposes of this specification and the following claims, the term "phr" (an acronym for parts per hundred parts of rubber) is used to indicate the weight parts of a given elastomeric compound component relative to 100 parts by weight of the elastomeric polymer, which is considered to exclude possible extension plasticizer oils.

[0087] Unless otherwise stated, all percentages are by weight. Brief description of the attached diagram

[0089] Please refer to the attached diagram:

[0090] - Figure 1 A schematic half-sectional view of a vehicle wheel tire according to the present invention is shown;

[0091] - Figure 2 Thermogravimetric analysis (TGA) plots of 2,5-disubstituted tetrazolium 1.1 and 1.3 are shown;

[0092] - Figure 3 It showed oligobutadiene IR spectra of 130 (3A) and its reaction product (3B) with tetrazolium 1.1;

[0093] - Figure 4 The oligobutadienes before (4A) and after (4B) the cycloaddition reaction with 1.1-disubstituted tetrazolium are shown. 130 H-NMR spectrum;

[0094] - Figure 5 It shows a product containing oligobutadiene Thermogravimetric analysis (TGA) trace of a sample of a mixture of 130 and 2,5-disubstituted tetrazolium 1.3;

[0095] - Figure 6 The images show the results before and after functionalization with the carbene precursor B 3-[4-(bromomethyl)phenyl]-3-(trifluoromethyl)-3H-bisacrylidine (III-a) (BPTD) from Example 2B. 130 (PV) H-NMR spectrum (DIAZ.: bisacrylidine aromatic signal; VIN.: vinyl bond);

[0096] - Figure 7 TGA analysis of the starting reagents (bisacrylidine III-a BPTD and tetrazolium 1.13) and the corresponding cross-linking functionalizing agent 3.1 synthesized according to scheme 43 is shown;

[0097] - Figure 8 The following are shown before and after heat treatment at 140°C, by dispersing the reagent 3.4 according to the invention in... IR spectra of the blends obtained in 130;

[0098] - Figure 9 Thermogravimetric analysis (TGA) plot of a sample with reagent 3.5 according to the present invention is shown. Invention Details

[0100] The first aspect of the present invention is represented by a crosslinking functionalizing agent of formula (I) for elastomer compounds:

[0101]

[0102] It contains at least a divalent organic linker residue A between the carbene precursor group B and the tetrazolium component.

[0103] The phrase "at least a divalent organic linker residue" is used to indicate a stable organic residue capable of covalently binding at least one tetrazolium and a group B.

[0104] Preferably, only one 2,5-disubstituted tetrazolium is present in the reagent of formula (I), i.e., n equals 1, and A is a divalent organic residue that links group B to a single tetrazolium. In this preferred embodiment, the reagent of formula (I) is characterized in that the individual activation temperature (T-Tetr) of the tetrazolium component is greater than the activation temperature (TB) of group B. Therefore, a preferred embodiment of the present invention is a crosslinking functionalizing agent of formula (I) for elastomer compounds:

[0105]

[0106] in

[0107] n is an integer equal to 1;

[0108] B is an organic group capable of producing carbene or nitrobenes.

[0109] A is a divalent organic residue linker between group B and tetrazolium, wherein A is covalently linked to tetrazolium at position 2 or 5;

[0110] R is an organic group covalently attached to the 5- or 2-position of the tetrazolium, selected from straight-chain or branched C1-C2 groups. 10 Alkyl; C6-C 20 Aryl; C3-C10 Cycloalkyl; a 5- or 6-membered saturated, unsaturated, or aromatic monocyclic or bicyclic fused heterocyclic group containing at least one heteroatom selected from N, S, and O, wherein R is optionally substituted with at least one electron-withdrawing group EW or at least one electron-donating group ED.

[0111] The cross-linking functionalized reagent of formula (I) is characterized by the activation temperature (TB) of group B and the activation temperature (T-Tetr) of tetrazolium, wherein the activation temperature (T-Tetr) is greater than the activation temperature (TB).

[0112] In the reagent of formula (I), in addition to having the function of attaching group B to one or more tetrazoles, the linking group A can also help to modulate the reactivity and physical properties of the reagent, such as the lipophilicity of the tetrazole component T-Tetr and group B and / or the activation temperature.

[0113] For these purposes, linker A must be a residue that is sufficiently stable under normal conditions of processing, vulcanization and use of the elastomer compound.

[0114] During the synthesis of cross-linking functionalized reagents, at the level of linker A, a link is typically achieved between a portion of the reagent containing a carbene or azine precursor B and another portion containing one or more 2,5-disubstituted tetrazolium.

[0115] Therefore, in addition to aromatic or heteroaromatic systems, linker A may contain optionally substituted aliphatic residues or (hetero)aromatic-aliphatic composite systems, and at least one linker functional group containing one or more heteroatoms, through which such linking can occur in the synthesis of crosslinking functionalized reagents.

[0116] Stable linking functional groups can be, for example, ethers, amino (preferably tert-amino), thioethers, trialkyl or triarylphosphine, silanes, amides (preferably secondary-amino), silazanes, phosphate esters, sulfonates, sulfoxide groups, or carbon chains, which can be obtained by coupling, for example, through Grignard, Wittig, Michael reactions, aldol condensation, etc., as known to those skilled in the art.

[0117] Organic residue A (linking group) may contain or consist of at least one of alkylene, arylene and / or heterocyclic groups or combinations thereof.

[0118] In this specification, alkylene, arylene, and heterocyclic groups refer to at least a divalent group obtained by removing at least one hydrogen atom from an alkyl, aryl, and heterocyclic group, respectively.

[0119] Connector A may optionally include or consist of at least one of the following: C1-C 20 Alkylene, preferably C1-C 10An alkylene group is a saturated or unsaturated, straight-chain or branched hydrocarbon residue that—in the chain—may include one or more heteroatoms, such as B, O, N, S, P or Si, and / or one or more linking functional groups as defined above, the alkylene group potentially being directly linked to a tetrazolium at the 2 or 5 position, or directly linked to a group B.

[0120] Alkyl groups can be, for example, -CH2-, -CH<, or -(CH2). 2-20 -, -CH2-O-CH2-, -CH2-Nalkyl-CH2-, -(Nalkyl-CH2-CH2)-; -(O-CH2-CH-alkyl)-, -CH2-S-CH2-, -(S-CH2-CH-alkyl)-, -SO-CH2-alkyl, -CH2-SO-CH2-, -SO2-CH2-alkyl, -CH2-SO2-CH2-, -P(alkyl)-CH2-alkyl, -CH2-P(alkyl3)-CH 2、 -SiH2-CH2-alkyl, -CH2-SiH2-CH2-.

[0121] At least one carbocyclic aromatic system of linker A can be at least one optionally substituted C6-C 20 Aryl groups, preferably C6-C 10 Arylene. Preferably, the arylene comprises a ring system of monocyclic and polycyclic aromatic carbon rings, wherein the individual carbon rings are fused or connected to each other by single bonds, and more preferably selected from phenylene, biphenylene, naphthylene, fluorene, phenantrilene, p-alkoxyphenylene, chlorophenylene, dichlorophenylene such as 3,5-dichlorophenylene.

[0122] The at least one subheterocyclic group in the linking group A, which contains at least one heteroatom selected from N, S, and O, can be a monocyclic or bicyclic 5- or 6-membered ring, saturated, unsaturated, or aromatic, optionally a benzofused compound, and optionally substituted. Preferably, the at least one subheterocyclic group is derived from pyrrole, dihydropyrrole, pyrrolidine, furan, dihydrofuran, tetrahydrofuran, benzofuran, isobenzofuran, dihydrobenzofuran, thiophene, dihydrothiophene, tetrahydrothiophene, benzothiophene, thiazole, dihydrothiazole, thiadiazole, dihydrothiadiazole, triazole, dihydrotriazole, benzotriazole, tetraazole, dihydrotetraazole, isothiazole, dihydroisothiazole, imidazole, benzimidazole, dihydroimidazolium, dihydrobenzimidazole, oxazole, dihydrooxazole, benzoxazole, dihydrobenzoxazole, dihydrobenzoxazole, oxazoline, isoxazole, dihydroisothi ... Oxazole, isoxazoline, oxadiazole, pyrazole, benzopyrazole, dihydropyrazole, pyridine, dihydropyridine, piperidine, piperazine, pyrazine, pyridazine, γ-pyran, tetrahydropyran, dihydropyran, 1,4-dioxane, benzo-1,4-dioxane, morpholine, thiomorphine, pyrazine, dihydropyrazine, pyrazoleline, quinoline, isoquinoline, dihydroquinoline, tetrahydroisoquinoline, indole, dihydroindole, isoindole, pyrimidine, dihydropyrimidine, quinazoline, quinoxaline, etc., more preferably derived from thiophene, pyrrole, furan, imidazole, oxazole, thiazole, pyridine, or pyrazoline.

[0123] In the reagent of formula (I) of the present invention, although not preferred, it is possible that a tetrazolium, which may be present as a substituent R in the linker A or even substituted or monosubstituted at other positions, is thermally stable at the activation temperature (T-Tetr) and vulcanization temperature (TV) of the tetrazolium component of the reagent of formula (I) of the present invention.

[0124] In a preferred embodiment, at least one of the arylene and / or heterocyclic groups of linker A is directly or by inserting a CH2- group to the tetrazolium. The applicant has observed that the presence of a (hetero)aromatic or (hetero)aromatic-CH2- system directly bound to the tetrazolium allows for a decrease in the activation temperature T-Tetr, and vice versa, the presence of an alkylene group as defined above directly bound to the tetrazolium allows for an increase in the activation temperature T-Tetr.

[0125] Preferably, the molecular weight of residue A is less than 1000 g / mol, more preferably less than 500 g / mol, even more preferably less than 300 g / mol, and even more preferably less than 250 g / mol.

[0126] Particularly preferred examples of residue A are shown below (in a preferred embodiment shown here, where they are bound to group B and a single tetrazolium, n=1):

[0127] β-p-phenylene-CH2-O-p-phenylene-tetrazole

[0128] β-p-phenylene-CH2-tetraazole

[0129] β-p-phenylene-CH2-O-m-phenylene-tetrazole

[0130] β-Phenylene-2,5-thienyl-tetrazole

[0131] B-(CH2)9-O-m-phenylene-tetraazole.

[0132] In the reagent of formula (I), the R group is preferably selected from optionally substituted aryl C6-C groups as defined above. 10 Or heterocyclic group.

[0133] The R group can be, for example, phenyl, 4-hydroxyphenyl, 4-carboxyphenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 3,5-dimethoxyphenyl, 2,4,5-trifluorophenyl, 4-octyloxyphenyl, 4-phenyl-1,2,4-triazolidine-3,5-dione-yl, 1-hexyl, 2-thienyl, 5-amino-2-thienyl, benzyl, diphenyl, pyrrole, or benzofused polycyclic aromatic residues derived from, for example, naphthalene, fluorene, or anthracene, optionally converted to, for example, halogen, nitrile, carboxyl, sulfonyl, C1-C 20 Alkyl or C1-C 20 Alkyl-substituted.

[0134] In a preferred embodiment, R is selected from phenyl, 3-chlorophenyl, 3,5-dichlorophenyl and thiophene.

[0135] R can be selected from several lipophilic groups, such as 4-hexyl-phenyl, naphthyl, fluorenyl, etc., to increase the solubility of the reagent of formula (I) in the elastomer matrix.

[0136] Alternatively, R can be selected to appropriately alter the activation temperature T-Tetr of the tetrazolium component, which is also due to suitable electron-withdrawing EW or electron-donating ED substituents.

[0137] The R group can be replaced by at least one electron-withdrawing group EW.

[0138] Generally, tetrazolium is more stable if R is replaced by an electron-withdrawing group EW, and the activation temperature T-Tetr increases if the R group is at the 5 position, and vice versa. If the R group is at the 2 position, tetrazolium becomes activated at a lower temperature.

[0139] The electron-withdrawing group (EW) can be selected, for example, from halogens, substituted carbonyl groups (-CO-alkyl or -CO-aryl), carboxyl groups, esters, cyano groups, nitro groups, haloalkyl groups, sulfonyl groups (SO2-alkyl or SO2-aryl), and haloalkyl groups. Preferably, the EW group is selected from esters, cyano groups, halogens, and haloalkyl groups.

[0140] When the R-group is bonded to the nitrogen atom at the 2-position of the tetrazolium, the R-group is preferably an EW group such as a halogen at the 3 and 5 positions, and more preferably a phenyl group bis-substituted with chlorine. The presence of these electron-withdrawing groups allows for the activation of the tetrazolium to be activated at relatively low temperatures.

[0141] Choosing an electron-withdrawing group (EW) may be advantageous, as the EW can be traced using appropriate analytical techniques (e.g., nuclear magnetic resonance) even when the reagent containing it of formula (I) is diluted in the elastomer compound, such as a fluorinated group, for example -CF3.

[0142] The R group can be substituted with at least one electron-donating group ED. Generally, if R is substituted with an electron-donating group ED, the tetrazolium becomes less stable, and if the R group is at the 5-position, the T-Tetr decreases, and vice versa if it is at the 2-position. The electron-donating group ED can be, for example, selected from hydroxyl, C1-C... 10 Alkoxy, benzyloxy, C1-C 10 Alkyl, amino, C1-C 10 Alkyl monosubstituted amino, C1-C 10 Alkyl disubstituted amino groups, primary amides (-NH-COR1), hydrazones (-CH=N-NR12), where R1 is H or a C1-C5 alkyl group, etc.

[0143] The reagent of formula (I) contains a carbene or azibene precursor group (B).

[0144] Suitable carbene precursor groups B are, for example, bisacrididine groups that release nitrogen upon heating, diazo groups, and ketenes that release CO.

[0145] The decomposition reaction of carbene precursor group B can be represented as follows:

[0146] Dipropion

[0147] Diazo R2-C(=N2)-Ar→R2-C:-Ar(+N2 or CO)

[0148] Enone R2-C(=C=O)-Ar

[0149] Where Ar represents an aromatic system of carbocyclic or heterocyclic rings, R2 is a perfluoroalkyl chain, preferably a CF3 group, which is a stable precursor B and can be traced by F-NMR.

[0150] In the reagent of formula (I), the carbene precursor group B is typically linked to at least one carbocyclic or heterocyclic aromatic system Ar at the carbon atom level that will form the carbene, said carbocyclic or heterocyclic aromatic system Ar being part of the linking group A.

[0151] Suitable nitrogen precursor groups B are, for example, sulfonyl azide groups, azides, which release nitrogen, isocyanates, and said nitrogen isocyanates release CO.

[0152] The decomposition reaction of the nitride precursor group B can be represented as follows:

[0153] Sulfonyl azide Ar-SO2-N3→Ar-SO2N:(+N2)

[0154] Azides R or Ar-N3 → R or Ar-N:(+N2)

[0155] Isocyanates Ar-N=C=O → Ar-N:(+CO)

[0156] In the reagent of formula (I), if group B is a carbene precursor or a sulfonyl azide precursor, then the linker A preferably contains at least one aromatic system directly bound to B - an arylene or heterocyclic group as defined above.

[0157] In the reagent of formula (I), if group B is a nitrobenzene precursor azide, then linker A may contain an alkylene or aromatic system as defined above—an arylene or heterocyclic group—that is directly bonded to B.

[0158] In one implementation, the reagent of formula (I) is the reagent of formula (Ia):

[0159]

[0160] Where n = 1 and where B, A and R take the meaning previously indicated for the reagents in formula (I).

[0161] Specific examples of cross-linking functionalizing agents of formula (Ia) are shown below:

[0162]

[0163] In one implementation, the reagent of formula (I) is the reagent of formula (Ib):

[0164]

[0165] Where n = 1 and where B, A and R take the meaning previously indicated for the reagents in formula (I).

[0166] Specific examples of cross-linking functionalizing agents of formula (Ib) are shown below:

[0167]

[0168] Preferably, the molecular weight of the reagent of formula (I) is less than 1000 g / mol, more preferably less than 600 g / mol.

[0169] In one embodiment, the reagent of formula (I) is a reagent of formula (Ia) or (I-b), wherein A is a divalent organic residue (linker) of formula A”-A', wherein

[0170] A” - directly binds to the B group - selected from C6-C 10 arylene groups, and optionally benzyl-fused monocyclic or bicyclic heterocyclic groups of aromatic compounds having a 5- or 6-membered ring containing at least one heteroatom selected from N, S, and O.

[0171] A' may not exist, or if it does exist, it contains C6-C as defined above. 10 -Asyl, aromatic heterocyclic, C1-C 10 -alkylene-oxy-C6-C 10 -Alearyl- or C1-C 10 -alkylene-oxy-aromatic heterocyclic group, and it is bound to a tetrazolium through the aromatic moiety.

[0172] A” and A' are preferably directly combined, without the insertion of connecting functional groups.

[0173] B is a carbene precursor group or a nitrobenzene precursor sulfonyl azide group, and other substituents may have the aforementioned meanings.

[0174] In one embodiment, the reagent of formula (I) is a reagent of formula (Ia) or (1-b), wherein

[0175] A is a divalent organic residue (linker) of the formula A”-A', where

[0176] A”- directly binds to the B- group-selected from C1-C 10 -alkylene-, C6-C 10 -arylene-, a heterocyclic group containing at least one heteroatom selected from monocyclic or bicyclic N, S, and O and having an optionally fused 5- or 6-membered ring, C1-C 10 -alkylene-C6-C 10 -Asaryl- and C1-C 10 alkylene-heterocyclic group,

[0177] A' may not exist, or if it does exist, it contains C6-C as defined above. 10 -Asyl, aromatic heterocyclic, C1-C 10 -alkylene-oxy-C6-C 10 -Alearyl- or C1-C 10 -alkylene-oxy-aromatic heterocyclic group, and it is bound to a tetrazolium through the aromatic moiety.

[0178] A” and A' preferably bind directly without inserting connecting functional groups.

[0179] B is the azide group, a nitrogen-bene precursor.

[0180] And the other substituents have the aforementioned meaning.

[0181] In a preferred embodiment, the reagent of formula (I) is a reagent of formula (Ia) or (Ib), wherein

[0182] R is selected from phenyl, halophenyl, (poly)halophenyl, and thiophene; and / or

[0183] B is selected from azides, trifluoromethylbisacrylidine, and sulfonyl azides.

[0184] In a more preferred embodiment, the reagent of formula (I) is a reagent of formula (Ia) or (Ib), wherein

[0185] A is a divalent organic residue (linker) of the formula A”-A', where

[0186] A”-directly binds to the B group-selected from C6-C 10 arylene, and optionally benzo[a] fused monocyclic or bicyclic heterocyclic group comprising at least one heteroatom selected from N, S, and O, having a 5- or 6-membered ring.

[0187] A' may not exist, or if it does exist, it contains C6-C as defined above. 10 -Asyl, aromatic heterocyclic, C1-C 10 -alkylene-oxy-C6-C 10 -Alearyl- or C1-C 10 -alkylene-oxy-aromatic heterocyclic group, and it is linked to a tetrazolium via the aromatic moiety, wherein A” and A’ are preferably directly linked without the insertion of a linker group.

[0188] R is selected from phenyl, halophenyl, (poly)halophenyl, and thiophene; and

[0189] B is selected from trifluoromethylbisacrylidine and sulfonyl azide.

[0190] In a more preferred embodiment, the reagent of formula (I) is a reagent of formula (Ia) or (Ib), wherein

[0191] A is a divalent organic residue (linker) of the formula A”-A', where

[0192] A”- directly binds to the B- group-selected from C1-C 10 -alkylene-, C6-C 10 -arylene-, a optionally benzene-fused heterocyclic group containing at least one heteroatom selected from monocyclic or bicyclic N, S, and O and having a 5- or 6-membered ring, C1-C 10 -alkylene-C6-C10 -Asaryl- and C1-C 10 alkylene-heterocyclic group,

[0193] A' may not exist, or if it does exist, it contains C6-C as defined above. 10 -Asyl, aromatic heterocyclic, C1-C 10 -alkylene-oxy-C6-C 10 -Alearyl- or C1-C 10 -alkylene-oxy-aromatic heterocyclic group, and it is bound to a tetrazolium through the aromatic moiety.

[0194] A” and A' are preferably directly bonded without the insertion of a connecting base.

[0195] R is selected from phenyl, halophenyl, (poly)halophenyl, and thiophene; and

[0196] B is the azide group, a nitrogen precursor.

[0197] In the reagent of formula (I), appropriate selection of organic residue A, group R, one or more possible electron-withdrawing substituents EW and / or electron-donating substituents ED, group B and its possible substituent R2 allows for specific tuning of the activation temperature (TB) of group B and the activation temperature (T-Tetr) of 2,5-disubstituted tetrazolium, in addition to altering its solubility in a pre-selected elastomeric matrix.

[0198] Preferably, the activation temperature TB of the carbene or azibene precursor in the B group of the reagent of formula (I) is less than 140°C, more preferably less than 135°C, and even more preferably less than 130°C.

[0199] Preferably, the activation temperature T-Tetr of one or more of the tetrazolium components of the reagent of formula (I) is not less than 140°C, more preferably not less than 150°C, and even more preferably not less than 160°C.

[0200] Preferably, the minimum difference between the activation temperature (T-Tetr) of the tetrazolium component and the activation temperature (TB) of group B is at least 20°C, more preferably at least 30°C, and even more preferably at least 40°C.

[0201] In a preferred embodiment characterized by a lower T-Tetr, the reagent of formula (I) is a reagent of formula (Ia) or (Ib), wherein A is a divalent organic residue (linker) of formula A”-A', wherein both the portion of A' that is directly bound to the tetrazolium and the substituent R on the tetrazolium are aromatic systems.

[0202] In another preferred embodiment characterized by higher T-Tetr, the reagent of formula (I) is a reagent of formula (Ia) or (Ib), wherein A is a divalent organic residue (linker) of formula A”-A', wherein both the portion A' directly bound to the tetrazolium and the substituent R on the tetrazolium are aliphatic.

[0203] The reagent of formula (I) can be prepared according to conventional procedures.

[0204] For the purposes of preparation, as shown in Scheme 2 below, in linker A, two parts can usually be identified, referred to herein as A' and A", which in the corresponding synthetic intermediates (II) and (III) can belong to the part containing 2,5-disubstituted tetrazolium and the part containing carbene or azinon precursor containing group B, respectively.

[0205] Therefore, the reagent of formula (I) can be prepared from the intermediates of formulas (II) and (III) according to the following general scheme 2, where n = 1, and for simplicity, it is referred to as BA-tetrazole-R in this paper:

[0206] Option 2

[0207]

[0208] in

[0209] B represents a carbene or azibene precursor as defined above.

[0210] "A" represents the part of the linker A that is directly bonded to B.

[0211] A' represents the remaining possible portion of the linker A that binds to a tetrazolium at position 2 or 5.

[0212] X represents a reactive group, such as a halogen, aryl or alkyl sulfonate, toluene sulfonate, methanesulfonate or trifluoromethanesulfonate.

[0213] Y represents a second reactive group capable of reacting with the reactive group X of intermediate (III) and thus stably binding A” to A', such as groups OH, NH, NH2, B(OH)2, or Sn(R3)3, where R3 represents a C1-C5 alkyl group.

[0214] Tetraazole refers to a tetraazole ring substituted at positions 2 and 5.

[0215] R represents an organic group as defined above, and

[0216] A is a linker containing residues A”-A’ that are covalently bonded to each other.

[0217] Residue A' may be optional, for example, in the case of reagent 3.2. The reaction between intermediates of formula (II) and (III) can be, for example, a nucleophilic substitution reaction, an alkylation reaction, or a coupling reaction, such as the Suzuki reaction, Stille reaction, Heck reaction, etc.

[0218] Based on the information provided herein, chemists skilled in the art can prepare the crosslinking functionalized reagent (I) of the present invention, determine suitable linker A, and identify suitable intermediates of formulas (II) and (III) for its synthesis.

[0219] These intermediates are commercially available or prepared as described in the literature or according to conventional methods, as illustrated in the experimental section of this application.

[0220] For example, the intermediate of formula (II) in which the R group is linked to a tetrazolium at the 2-position can be prepared according to the following scheme 3 (intermediate II-a) and converted into the corresponding cross-linking functionalizing agent (Ia):

[0221] Option 3: Synthesis from aldehyde via hydrazone (a1) (R at position 2, BA- at position 5)

[0222]

[0223] The aldehyde (V) reacts with an acylhydrazine (in this case, toluenesulfonylhydrazine) to give a toluenesulfonylhydrazone (IV), which is cyclized in the presence of a suitable amine R-NH2 (VIII) to give a tetrazolium intermediate (II-a). Subsequently, the tetrazolium intermediate (II-a) – by reacting with intermediate (III) – ultimately provides a cross-linking functionalizing agent (Ia).

[0224] Similarly, the intermediate of formula (II) can be prepared according to scheme 4 below (where the R group is instead combined with a tetrazolium at position 5 (intermediate II-b)) and converted into the corresponding cross-linking functionalizing agent (Ib):

[0225] Option 4: Synthesis from aldehyde via hydrazone (a2) (R at position 5, BA- at position 2)

[0226]

[0227] The aldehyde (V) reacts with an acylhydrazine (in this case, toluenesulfonylhydrazine) to give a toluenesulfonylhydrazone (IV), which is cyclized in the presence of a suitable amine Y-A'-NH2 (VIII) to give a tetrazolium intermediate (II-b). Subsequently, the tetrazolium intermediate (II-b) reacts with intermediate (III) to ultimately provide a cross-linking functionalizing agent (Ib). Alternatively, the intermediate of formula (II) (where the R group is linked to a tetrazolium at position 5 (intermediate II-b)) can be prepared according to scheme 5 below and converted into the corresponding cross-linking functionalizing agent (Ib):

[0228] Option 5:

[0229] (b1) was synthesized from nitrile (VII) via a two-step alkylation process (R at position 5, BA- at position 2).

[0230]

[0231] Wherein Z represents a halogen or sulfonate, toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, B(OH)₂, and other substituents have the above meanings, wherein the preselected nitrile R-CN is cyclized to a monosubstituted tetrazolium (VI), alkylated to obtain a tetrazolium intermediate (II-b), which ultimately provides a functionalized crosslinking agent (Ib) for introducing the B moiety by reacting with intermediate (III). In this synthetic route, targeted protection and deprotection of reactive groups as known to those skilled in the art are optionally used. The Z and Y groups must be appropriately selected to obtain proper selectivity and successful reactions, and to minimize unwanted reactions.

[0232] Alternatively, the tetrazolium intermediate (VI) can be alkylated by reacting with intermediate XAB(III), thus introducing the entire AB moiety directly at the 2-position of the tetrazolium, as shown in Scheme 6 below.

[0233] Option 6:

[0234] (b2) was synthesized from nitrile via alkylation in a single step (R at position 5, BA- at position 2).

[0235]

[0236] Intermediates of formula (III)B-A'-X or BAX can be prepared by conventional methods, or they can be commercially available.

[0237] If the starting product or intermediate contains functional groups that interfere with the synthesis, the groups can be appropriately protected and deprotected, for example, as described in the book "Protective Groups in Organic Chemistry" by publisher J.F.W. McOmiie (1973).

[0238] Another aspect of the invention is represented by a functionalized diene elastomer polymer, which is obtained by reacting the diene elastomer polymer with at least one reagent of formula (I) as defined above.

[0239] Functionalized diene elastomer polymers are prepared according to the following method, wherein the method preferably includes:

[0240] -Provides diene elastomer polymers;

[0241] - Provide reagents of formula (I) as defined above,

[0242] - Mix the diene elastomer polymer and the reagent of formula (I), and keep the blend at a temperature below 170°C, preferably below 160°C, preferably for a period of 1 to 10 minutes, more preferably 2 to 4 minutes, to obtain a functionalized diene elastomer polymer.

[0243] Functionalized polymers can be further mixed separately or in situ with other components in the rubber compound and then vulcanized.

[0244] Preferably, in the mixer, more preferably in at least one tangential rotor type Or in a closed mixer with a mixing rotor, or in a Ko-Kneader TM type The functionalization of the diene elastomer polymer according to the invention is carried out in a continuous mixer of either a twin-screw or multi-screw type.

[0245] Preferably, in the functionalization method of the diene elastomer polymer of the present invention, the reagent of formula (I) is used at a weight percentage of 0.1% to 10%, more preferably 0.5% to 3%, relative to the diene elastomer polymer.

[0246] Preferably, the diene elastomer polymer to be functionalized according to the method of the present invention is selected from natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), including rubbers whose chain ends are already functionalized. Furthermore, diene polymers even poorly reactivity in vinyl groups, such as partially hydrogenated styrene-butadiene rubber, bromobutyl rubber (BIIR), chlorobutyl rubber (CIIR), and isobutylene-isoprene rubber (IIR), can be readily functionalized due to the significant reactivity of the carbene or azibene obtained from the decomposition of the B group in the reagent of formula (I).

[0247] Advantageously, the functionalized diene elastomer polymer of the present invention can improve the properties of the elastomer compound in which it is incorporated by increasing crosslinking and—in the case of dissimilar polymer blends—their optimal compatibility, as demonstrated in this experimental section.

[0248] Another object of the present invention is an elastomer composition for tire rubber compounds comprising the reagent of formula (I) above.

[0249] The elastomer composition for tire rubber according to the invention is characterized by one or more of the following preferred aspects, either individually or in combination with each other.

[0250] The elastomeric composition according to the invention comprises at least one diene elastomeric polymer in 100 phr. The elastomeric composition according to the invention may comprise two or more diene elastomeric polymers in blend form, totaling 100 phr. The diene elastomeric polymer may be selected from those elastomeric compositions commonly used and particularly suitable for the production of tires that can be vulcanized with sulfur, i.e., from solid elastomeric polymers or copolymers having unsaturated chains with a glass transition temperature (Tg) typically less than 20°C, preferably in the range of 0°C to 110°C.

[0251] These polymers or copolymers may be of natural origin, or they may be obtained by solution polymerization, emulsion polymerization, or gas-phase polymerization of one or more conjugated dienes, optionally mixed with at least one comonomer selected from monoolefins, monovinyl aromatics, and / or polar comonomers in an amount not exceeding 60% by weight. The conjugated dienes typically contain 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, and they may be selected, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, and mixtures thereof. 1,3-butadiene and isoprene are particularly preferred.

[0252] Monoolefins may be selected from ethylene or α-olefins that typically contain 3-12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or mixtures thereof.

[0253] Monovinyl aromatic hydrocarbons, which may optionally be used as comonomers, typically contain 8 to 20, preferably 8 to 12, carbon atoms and may be selected, for example, from: styrene; 1-vinylnaphthalene; 2-vinylnaphthalene; various alkyl, cycloalkyl, aryl, alkylaryl, or styrene-arylalkyl groups, such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenylbutyl)styrene, and mixtures thereof. Styrene is particularly preferred.

[0254] The polar comonomers that can be used optionally may be selected from: vinylpyridine, vinylquinoline, acrylic acid and alkyl acrylates, acrylonitrile or mixtures thereof, such as methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile and mixtures thereof.

[0255] Preferably, the diene elastomer polymer may be derived from, for example, cis-1,4-polyisoprene (natural or synthetic, preferably natural rubber), 3,4-polyisoprene, polybutadiene (especially polybutadiene with a high 1,4-cis content), optionally halogenated isoprene / isobutene copolymers, 1,3-butadiene / acrylonitrile copolymers, styrene / 1,3-butadiene copolymers, styrene / isoprene / 1,3-butadiene copolymers, and mixtures thereof.

[0256] The elastomer composition may optionally comprise at least one polymer of one or more monoolefins and olefin comonomers or derivatives thereof. The monoolefin may be selected from: ethylene and α-olefins, typically containing 3-12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or mixtures thereof. Preferred are: copolymers of ethylene and α-olefins, optionally with dienes; homopolymers of isobutene, optionally at least partially halogenated, or copolymers thereof with a small amount of diene. The optionally present diene typically contains 4-20 carbon atoms and is preferably selected from: 1,3-butadiene, isoprene, 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethimide-2-norbornene, 5-methylene-2-norbornene, vinylnorbornene, or mixtures thereof. Among them, the following are particularly preferred: ethylene / propylene copolymer (EPR) or ethylene / propylene / diene copolymer (EPDM); polyisobutylene; butyl rubber; halogenated butyl rubber, especially chlorobutyl rubber or brominated butyl rubber; and mixtures thereof.

[0257] The elastomer composition may optionally contain one or more partially hydrogenated diene elastomer polymers.

[0258] The elastomeric tire composition according to the invention comprises at least one reinforcing filler.

[0259] The compositions of the present invention may contain at least one reinforcing filler of 1 phr to 150 phr, 5 phr to 120 phr, or 10 phr to 90 phr.

[0260] Preferably, the reinforcing filler is selected from carbon black, white filler, silicate fibers, lignin, cellulose, or mixtures thereof. In one embodiment, the reinforcing filler is a white filler selected from hydroxides, oxides or hydrated oxides, salts and hydrated metal salts, modified silicate fibers, or mixtures thereof. Preferably, the white filler is silica.

[0261] Preferably, the silica may be present in the elastomer composition in an amount of 1 phr to 100 phr, more preferably 30 phr to 70 phr.

[0262] Suitable commercial examples of conventional silica are Zeosil 1165MP manufactured by Solvay and Ultrasil 7000GR manufactured by Evonik.

[0263] In one embodiment, the reinforcing filler is carbon black.

[0264] Preferably, the carbon black is present in the elastomer composition in an amount of 1 phr to 100 phr, more preferably 5 phr to 70 phr.

[0265] Preferably, the carbon black is selected from materials with a surface area (established according to ISO 18852:2005 standard by STSA-statistical thickness surface area) of not less than 20 m². 2 / g, preferably greater than 50m 2 Those with / g.

[0266] Carbon black can be, for example, N234, N326, N330, N375 or N550, N660 sold by Birla Group (India) or Cabot Corporation.

[0267] The elastomer composition for tire rubber of the present invention comprises at least one agent of formula (I).

[0268] Preferably, the elastomer composition of the present invention contains at least one reagent of formula (I) in an amount of at least 0.3 phr, at least 0.5 phr, at least 0.7 phr, or at least 1 phr.

[0269] The elastomer composition for tire rubber of the present invention preferably contains at least one reagent of formula (I) in no more than 10 phr, more preferably no more than 5 phr, and even more preferably no more than 2 phr.

[0270] The elastomer composition for tire rubber of the present invention preferably contains at least one agent of formula (I) in the form of 0.1 phr to 10 phr, more preferably 0.3 phr to 5 phr, and even more preferably 0.5 phr to 3 phr.

[0271] The elastomer composition for tire rubber of the present invention may contain two or more crosslinking functionalizing agents of formula (I) in the blend, preferably in a total amount of 0.1 phr to 10 phr, more preferably 0.3 phr to 5 phr, and even more preferably 0.5 phr to 3 phr.

[0272] The elastomer composition for tire rubber compounds according to the present invention may contain a vulcanizing agent.

[0273] Preferably, the composition contains at least one vulcanizing agent at a concentration of at least 0.1 phr, at least 0.2 phr, at least 0.5 phr, at least 0.8 phr, or at least 1 phr.

[0274] Preferably, the composition comprises at least one vulcanizing agent in the form of 0.1 to 10 phr, 0.2 to 10 phr, 1 to 10 phr, or 1.5 to 5 phr.

[0275] At least one vulcanizing agent is preferably selected from sulfur, or from sulfur-containing molecules (sulfur donors), such as bis[(trialkoxy)propyl] polysulfide, thiuram, dithiodimorpholine and caprolactam-disulfide and mixtures thereof.

[0276] In one embodiment, the vulcanizing agent is selected from the polytetraazole crosslinking agent described in patent application WO2021 / 137143A1 representing the applicant.

[0277] Preferably, the vulcanizing agent is sulfur, preferably selected from soluble sulfur (crystalline sulfur), insoluble sulfur (polymerized sulfur), and sulfur dispersed in oil and mixtures thereof.

[0278] A commercial example of a vulcanizing agent suitable for the elastomer compositions of the present invention is Redball Superfine from International Sulfur Inc.

[0279] In the elastomer compositions of the present invention, the vulcanizing agent may be used in conjunction with auxiliaries known to those skilled in the art, such as vulcanization activators, accelerators and / or retarders.

[0280] The elastomer composition according to the invention may optionally contain at least one vulcanization activator.

[0281] The vulcanization activators suitable for the elastomer compositions of the present invention are zinc derivatives, particularly ZnO, ZnCO3, and salts of saturated or unsaturated fatty acids containing 8-18 carbon atoms, preferably formed in situ in the elastomer composition by the reaction of ZnO and fatty acids. The same applies to Bi2O3, PbO, Pb3O4, PbO2, or mixtures thereof. For example, zinc stearate (preferably formed in situ from ZnO and fatty acids), or magnesium stearate (formed from MgO), or mixtures thereof, can be used in the elastomer composition.

[0282] The vulcanization activator may preferably be present in the elastomer composition of the present invention in an amount of 0.2 phr to 15 phr, more preferably 1 phr to 5 phr.

[0283] The preferred activator is derived from the reaction of zinc oxide and stearic acid.

[0284] An example of an activator is Aktiplast ST, a product sold by RheinChemie.

[0285] The elastomer composition according to the invention may further contain at least one vulcanization accelerator.

[0286] Commonly used vulcanization accelerators can be selected from, for example, dithiocarbamates, guanidines, thioureas, thiazoles, sulfenamides, sulfenamides, thiurams, amines, xanthan gum, or mixtures thereof.

[0287] Preferably, the accelerator is selected from mercaptobenzothiazole (MBT), N-cyclohexyl-2-benzothiazole-sulfenamide (CBS), N-tert-butyl-2-benzothiazole-sulfenamide (TBBS), and mixtures thereof.

[0288] A commercial example of an accelerator suitable for this elastomer composition is N-cyclohexyl-2-benzothiazole-sulfenamide. (CBS or CZ) and N-tert-butyl-2-benzothiazole sulfenamide, sold by Lanxess NZ / EGC.

[0289] The vulcanization accelerator can preferably be used in the elastomer composition of the present invention in an amount of 0.05 phr to 10 phr, more preferably 0.1 phr to 7 phr, and more preferably 0.5 phr to 5 phr.

[0290] The elastomer composition according to the invention may optionally contain at least one vulcanization retarder.

[0291] The vulcanization retarder suitable for this elastomer composition is preferably selected from urea, phthalic anhydride, N-nitrosodiphenylamine, N-cyclohexylthiophthalimide (CTP or PVI) and mixtures thereof.

[0292] A commercial example of a suitable delaying agent is Lanxess's N-cyclohexylthiophthalimide VULKALENTG.

[0293] The vulcanization retarder may preferably be present in the elastomer composition of the present invention in an amount of 0.05 phr to 2 phr.

[0294] The elastomer composition may contain one or more vulcanization delay agents as defined above in the mixture.

[0295] The elastomer composition according to the invention may optionally contain at least 0.05 phr, preferably at least 0.1 phr or 0.5 phr, more preferably at least 1 phr or 2 phr of at least one silane coupling agent.

[0296] Preferably, the elastomer composition according to the invention comprises at least one silane coupling agent in amounts of 0.1 phr to 20.0 phr or 0.5 phr to 10.0 phr, or even more preferably 1.0 phr to 5.0 phr.

[0297] Preferably, the coupling agent is selected from silane coupling agents having at least one hydrolyzable silane group, which can be represented, for example, by the following general formula (IX):

[0298] (R')3Si-C n H 2n -T(IX)

[0299] The R' groups may be the same as or different from each other, and are selected from alkyl, alkoxy, or aryloxy groups, or from halogen atoms, provided that at least one of the R' groups is an alkoxy or aryloxy group; n is an integer from 1 to 6; T is a group selected from the following: nitroso, mercapto, amino, epoxy, vinyl, imide, chlorine, -(S). m C n H 2n -Si-(R')3 and -S-COR', where m and n are integers from 1 to 6, and the R' group is as defined above.

[0300] Particularly preferred silane coupling agents are bis(3-triethoxysilylpropyl)tetrasulfide and bis(3-triethoxysilylpropyl)disulfide, also known as polysulfide compatibilizers. These coupling agents can be added as is or mixed with inert fillers (e.g., carbon black) to facilitate their incorporation into the elastomer composition.

[0301] An example of a silane coupling agent is TESPT: bis(3-triethoxysilylpropyl)tetrasulfide Si69 sold by Evonik.

[0302] The elastomer composition according to the invention may further comprise one or more industrially common additives, such as plasticizers, resins, antioxidants and / or anti-ozone agents (anti-aging agents), waxes, adhesives, etc.

[0303] For example, to further improve the processability of the rubber compound, the elastomer composition according to the invention may further contain at least one plasticizing oil.

[0304] The amount of plasticizer is preferably from 1 phr to 80 phr, more preferably from 10 phr to 70 phr, and even more preferably from 30 phr to 50 phr.

[0305] The term "plasticized oil" is used to refer to petroleum-derived processed oils, mineral oils, oils of plant origin, oils of synthetic origin, or combinations thereof.

[0306] Plasticizing oil can be a petroleum-derived processed oil selected from alkanes (saturated hydrocarbons), cycloalkanes, polycyclic aromatic hydrocarbons and mixtures thereof.

[0307] Suitable examples of petroleum-derived processed oils are aromatic, alkane, and naphthenic oils, such as industrially known MES (mildly extracted solvates), DAE (distillate aromatic extracts), TDAE (treated distillate aromatic extracts), TRAE (treated residual aromatic extracts), and RAE (residual aromatic extracts).

[0308] Plasticized oils can be oils derived from natural or synthetic sources of glycerol and fatty acid esters, including glycerol, triglycerides, diglycerides, monoglycerides, or mixtures thereof.

[0309] Examples of suitable vegetable oils are sunflower oil, soybean oil, flaxseed oil, rapeseed oil, castor oil, and cottonseed oil.

[0310] Plasticizing oil can be a synthetic oil selected from alkyl or aryl esters of phthalic acid or phosphoric acid.

[0311] The elastomer composition of the present invention may further comprise at least one resin, which, if used in the composition, is a non-reactive resin, preferably selected from hydrocarbon resins, phenolic resins, natural resins, and mixtures thereof.

[0312] The amount of resin can be from 0 phr to 80 phr, preferably from 10 phr to 40 phr.

[0313] The elastomeric composition according to the invention may optionally contain at least one wax.

[0314] The wax can be, for example, a mixture of petroleum wax or paraffin wax.

[0315] Commercial examples of suitable waxes are Repsol's n-chain alkanes and Rhein Chemie's microcrystalline waxes. A mixture of 654.

[0316] The wax may be present in the elastomer composition of the present invention in a total amount of 0.1 phr to 20 phr, preferably 0.5 phr to 10 phr, more preferably 1 phr to 5 phr.

[0317] The elastomer composition according to the invention may optionally contain at least one antioxidant.

[0318] The antioxidant is preferably selected from N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine (6PPD), N,N'-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine (77PD), N,N'-bis-(1-ethyl-3-methylpentyl)-p-phenylenediamine (DOPD), N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine, and N,N'-diphenyl-p-phenylenediamine (DP). N,N'-xylyl-p-phenylenediamine (DTPD), N,N'-di-β-naphthyl-p-phenylenediamine (DNPD), N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine (44PD), N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-1-methylpentyl-p-phenylenediamine, and mixtures thereof, preferably N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine (6-PPD).

[0319] A commercial example of a suitable antioxidant is Eastman's 6PPD.

[0320] The antioxidant may preferably be present in the elastomer composition in a total amount of 0.1 phr to 20 phr, more preferably 0.5 phr to 10 phr.

[0321] Another aspect of the invention is an elastomeric compound for tires obtained by mixing and possibly vulcanizing the elastomeric composition according to the invention.

[0322] As described below, depending on the conditions applied (mixing and vulcanization temperature TV), the preparation stage, and the characteristic activation temperature (TB, T-Tetr) of the reagent of formula (I), the resulting elastomer compound can have different properties, namely, non-crosslinkable and non-vulcanizable (not yet containing neither functionalized diene elastomer polymer nor vulcanizing agent), non-crosslinkable but vulcanizable (containing vulcanizing agent but not functionalized diene elastomer polymer), crosslinkable but non-vulcanizable (containing functionalized diene elastomer polymer but not vulcanizing agent), crosslinkable and vulcanizable (containing both functionalized diene elastomer polymer and vulcanizing agent), crosslinkable and vulcanizable (crosslinking the functionalized diene elastomer polymer but not vulcanizing), crosslinkable and vulcanizable (vulcanizing the functionalized diene elastomer polymer but not crosslinking), or finally crosslinkable and vulcanizable (crosslinking and vulcanizing the functionalized diene elastomer polymer).

[0323] Advantageously, the elastomer compound according to the invention can be readily processed prior to vulcanization. When vulcanized, the elastomer compound exhibits excellent properties comparable to those of similar compounds containing commercially available functionalized polymers, and even better than those containing non-functionalized diene elastomer polymers, as shown in this experimental section.

[0324] For example, compared to similar rubber compounds containing nonfunctionalized elastomer polymers, the crosslinked and vulcanized elastomer rubber compounds of the present invention can increase the E' value by at least 5% or even 10% at 10 Hz and 70 °C, while still at 70 °C, the tanδ value decreases by 5% or even 10%, as measured in the experimental section.

[0325] Another aspect of the present invention is a method for preparing an elastomer compound according to the present invention.

[0326] This method typically includes one or more mixing steps in at least one suitable mixer, particularly at least one mixing step (i) (non-productive) and one mixing step (ii) (productive) as defined above, followed by a final vulcanization step and an optional crosslinking step (iii).

[0327] Each mixing step may include several intermediate processing stages, characterized by temporarily suspending mixing to allow the addition of one or more components but not typically unloading the rubber compound.

[0328] A preferred method for preparing the elastomer compound according to the present invention includes:

[0329] -(i) A mixing step in one or more stages as defined above, wherein the temperature T1 is between 100°C and 170°C (non-productive step);

[0330] -(ii) The step of adding and mixing the vulcanizing agent as defined above, wherein the temperature T2 is between 50°C and 120°C (production step), and

[0331] -(iii) The vulcanization and optional crosslinking steps as defined above, wherein the temperature T3 is between 140°C and 190°C, to obtain the vulcanized and optional crosslinked elastomer compound according to the invention.

[0332] Depending on the activation temperature (TB) of group B and one or more activation temperatures (T-Tetr) of the tetrazolium component (which can be adjusted by appropriately selecting suitable R substituents, linker A and possible R2 substituents), the elastomer polymer functionalization reaction can be carried out prior to subsequent vulcanization and optional crosslinking reactions.

[0333] After in-situ functionalization, the functionalized diene elastomer polymer can thus be readily incorporated into the elastomer mixture until it is fully dispersed, by reacting a common commercial polymer with the reagent of formula (I) at normal mixing temperatures and in a simple mixer, without encountering mixing difficulties that may result from material thickening caused by undesirable crosslinking.

[0334] Subsequently, only when the mixture reaches a satisfactory homogeneity can the material be directly consolidated in the mold through classical sulfur vulcanization and optionally through the activation of tetrazolium reaction of the functionalized diene elastomer polymer.

[0335] During the first mixing step (i), the reinforcing filler and the reagent of formula (I) are dispersed into the elastomer matrix at a temperature T1. Under these conditions, at least one tetrazolium ring of the reagent of formula (I) remains substantially stable and does not undergo significant decomposition, while the B-group carbene or azibene precursor of the reagent of formula (I) decomposes and reacts with the elastomer matrix, thus functionalizing the least reactive polymer.

[0336] In the subsequent productive step (ii), which takes place at a temperature T2 where both the tetrazolium component and the vulcanizing agent are stable, the vulcanizing agent is preferably dispersed together with the vulcanization accelerator and / or retarder. In the productive step (ii), the temperature T2 is typically maintained below 120°C, preferably below 100°C, to avoid any undesirable pre-vulcanization.

[0337] Finally, in the final step (iii), the vulcanizable and crosslinkable rubber compound is incorporated into one or more parts of the tire and subjected to vulcanization, preferably in a mold at a temperature T3, wherein the rubber compound is consolidated by both crosslinking (through the decomposition of the tetrazolium component and the subsequent reaction of the acrylonitrile imine intermediate with the polymer double bond) and by forming a sulfur bridge (polar) of the vulcanizing agent.

[0338] In one alternative, at least one of the activation temperatures (T-Tetr) of the tetrazolium component is higher than the vulcanization temperature (TV). Therefore, if it is heated to a temperature T3 above the vulcanization temperature (TV) but below the temperature of at least one T-Tetr in the final step (iii) of the method, a vulcanized but only partially crosslinked or uncrosslinked compound can be obtained, taking into account that the tetrazolium functional groups are not activated or only partially activated, and therefore do not react or react incompletely.

[0339] When the temperature of the tire during use exceeds one or more of the activation temperatures T-Tetr of the unreacted tetrazolium component, such a compound, when properly incorporated into tire components (e.g., the tread), can crosslink and thus solidify.

[0340] In this method, mixing steps (i) and (ii) are preferably performed in a conventional mixer.

[0341] For example, an open mill type mixer or a tangential rotor type mixer can be used. Type or hybrid rotor type of closed mixer, or Ko-Kneader TM type Mixing can be carried out in a continuous mixer of twin-screw or multi-screw type.

[0342] Preferably, the mixing steps are performed for different durations, such as 90 seconds to 600 seconds.

[0343] Another aspect of the present invention is a vehicle wheel tire component comprising or preferably composed of an elastomeric compound according to the present invention, wherein the vehicle wheel tire component is preferably selected from the tread, underlayer, wear-resistant layer, sidewall, sidewall insert, micro sidewall, liner, underliner, coating layer, bead filler, bead reinforcement layer (outer bead wrapping) and bead protection layer (bead wrapping), and more preferably selected from the tread, underlayer, coating layer and sidewall insert.

[0344] Tire components may comprise, or preferably comprise, uncrosslinked and / or unvulcanized elastomer mixtures (raw components) according to the invention or vulcanized and optionally crosslinked elastomer compounds according to the invention.

[0345] Another aspect of the invention is a vehicle wheel tire that includes at least one tire component according to the invention.

[0346] The vehicle wheel tire of the present invention may include at least one tire component, said tire component being composed of an uncured and / or uncrosslinked elastomeric compound according to the present invention (green tire) or a vulcanized and optionally crosslinked elastomeric compound according to the present invention (vulcanized tire).

[0347] Preferably, the component is selected from the tread, the base layer, the rubber layer, and the sidewall insert.

[0348] In one embodiment, the vehicle tire according to the invention comprises at least:

[0349] - A carcass structure comprising at least one carcass layer having opposing lateral edges associated with a corresponding bead structure;

[0350] - A pair of sidewalls, each sidewall optionally including a sidewall insert, the sidewall insert being applied to a side surface of the carcass structure at an axially external position;

[0351] -Optionally, a belt structure applied in a radial position outside the carcass structure;

[0352] - The tread, which is applied radially to the outside of the carcass structure or belt structure (if present),

[0353] - Optionally, an elastomeric material layer, the bottom layer, is applied at a radially inward location relative to the tire crown.

[0354] At least one component, preferably the crown, at least one carcass layer of rubber or sidewall insert, comprises or is preferably composed of an elastomeric compound according to the invention.

[0355] The tires according to the present invention can be tires for two-wheeled, three-wheeled or four-wheeled vehicles.

[0356] In one embodiment, the tire according to the invention is a car tire, preferably a high-performance car tire.

[0357] In one embodiment, the tire according to the invention is a motorcycle tire, wherein at least one component comprises or is preferably composed of an elastomeric compound according to the invention.

[0358] In a preferred embodiment, the tire according to the invention is a tire for motorcycle wheels, preferably a tire for sports or racing motorcycles.

[0359] Typically, motorcycle wheel tires are tires with a straight cross-section characterized by high lateral curvature.

[0360] The tires according to the invention can be used in summer or winter or in all seasons.

[0361] In one embodiment, the tire according to the invention is a tire for bicycle wheels.

[0362] Bicycle wheel tires typically include a carcass structure and a tread, the carcass structure being rolled up around a pair of circles at the rim at the bead, and the tread being disposed in a position radially outward of the carcass structure. Preferably, at least the tread and / or the rubber coating layer comprises an elastomeric compound according to the invention.

[0363] The tire according to the present invention can be manufactured according to a method including the following steps:

[0364] - A component for forming a green tire on at least one forming drum;

[0365] - To bond, mold, and vulcanize tires;

[0366] At least one of the components forming the green tire includes:

[0367] - Provide at least one raw component, said raw component comprising or preferably consisting of the vulcanizable elastomer compound of the present invention.

[0368] Description of tires according to the present invention

[0369] exist Figure 1 The image shows a vehicle wheel tire according to the invention in a radial half-section, which includes at least one component comprising the elastomeric compound of the invention.

[0370] exist Figure 1 In this context, "a" indicates the axial direction, and "X" indicates the radial direction; specifically, XX represents a straight line along the equatorial plane. For simplicity, Figure 1Only a portion of the tire is shown; the rest (not shown) are identical and arranged symmetrically with respect to the equatorial plane “XX”.

[0371] The tire (100) for a four-wheeled vehicle includes at least one carcass structure, the carcass structure including at least one carcass layer (101) having respective opposing end flaps, the end flaps being engaged to a corresponding annular anchoring structure (102), the annular anchoring structure (102) being referred to as a band, optionally associated with a bead filler (104).

[0372] The area of ​​the tire containing the band (102) and filler (104) forms a bead structure (103) designed to anchor the tire to the corresponding mounting rim (not shown).

[0373] The carcass structure is typically radial, meaning that the reinforcing element of at least one carcass ply (101) is located in a plane including the axis of rotation of the tire and substantially perpendicular to the equatorial plane of the tire. This reinforcing element is typically composed of fabric cords. Each bead structure is associated with the carcass structure by folding the opposite side edges of at least one carcass ply (101) rearward around an annular anchoring structure (102) to form a shape such that… Figure 1 The so-called tire body flange shown is (101a).

[0374] In one embodiment, a second carcass layer (applied at an axially outer position relative to the first carcass layer) can be used. Figure 1 (Not shown in the image), providing the connection between the carcass structure and the bead structure.

[0375] Optionally, a wear-resistant layer (105) made of an elastomeric material is disposed at an external location of each bead structure (103).

[0376] The carcass structure is associated with a belt structure (106), which includes one or more belt layers (106a), (106b) arranged to be radially stacked relative to each other and relative to the carcass layer, the belt layers typically having fabric and / or metal reinforcing cords incorporated within an elastomeric material layer.

[0377] These reinforcing cords can have a cross orientation relative to the circumferential extension direction of the tire (100). The term "circumferential" is used to indicate a direction that is typically oriented according to the tire's rotational direction.

[0378] At least one zero-degree reinforcement layer (106c), typically referred to as “belt 0°”, may be applied to the belt layers (106a) and (106b) at the radially outermost position. These layers typically incorporate multiple elongated reinforcement elements, usually metal or fabric cords, oriented in a substantially circumferential direction, thus forming an angle of several degrees (e.g., between about 0° and 6°) relative to a direction parallel to the tire equatorial plane, and are coated with a vulcanized elastomer material.

[0379] The tread (109) comprising the elastomeric compound according to the invention is applied at a position radially outside the belt structure (106).

[0380] On the side surfaces of the carcass structure, each side surface extends from one of the side edges of the tread (109) to the corresponding bead structure (103), and in the axially external position, a corresponding sidewall (108) made of elastomeric material is also applied.

[0381] In the radially outer position, the tread (109) has a rolling surface (109a) intended to contact the ground, and circumferential grooves are provided by lateral notches ( Figure 1 (Not shown) is connected to define a plurality of blocks of different shapes and sizes distributed on a rolling surface (109a), the circumferential groove of which is typically formed on the surface (109a). For simplicity, the surface (109a) is... Figure 1 The middle part is represented as smooth.

[0382] The bottom layer (111) can be arranged between the belt structure (106) and the tire crown (109).

[0383] Strips (110) of elastomeric material, commonly referred to as “micro-sidewalls,” may optionally be present in the connection region between the sidewalls (108) and the crown (109). These micro-sidewalls are typically obtained by co-extrusion with the crown (109) and allow for improved mechanical interaction between the crown (109) and the sidewalls (108). Preferably, the ends of the sidewalls (108) directly cover the side edges of the crown (109).

[0384] In the case of tubeless tires, a rubber layer (112) commonly referred to as the “liner” provides the necessary impermeability to the tire’s inflation air and may also be located in a radially inward position relative to the carcass layer (101).

[0385] The rigidity of the tire sidewall (108) can be improved by providing a reinforcing layer (120) to the bead structure (103) that is commonly referred to as a "flipper" or an additional strip insert.

[0386] The outer bead wrap (120) is a reinforcing layer that is wound around the respective bead core (102) and bead filler (104) to at least partially surround them, the reinforcing layer being disposed between at least one carcass layer (101) and the bead structure (103). Typically, the outer bead wrap is in contact with said at least one carcass layer (101) and said bead structure (103).

[0387] The outer sheath fabric (120) typically includes multiple fabric cords incorporated within an elastomer material layer.

[0388] The tire's annular reinforcement structure or bead (103) may include an additional protective layer, commonly referred to by the term "bead wrap" (121) or protective strip, and has the function of increasing the rigidity and integrity of the bead structure (103).

[0389] The bead wrap (121) typically includes multiple cords incorporated within a rubberized layer of elastic material, which are typically made of textile materials (e.g., aramid or rayon) or metal materials (e.g., steel cords).

[0390] Layers or sheets made of elastomeric material may be arranged between the belt layer structure and the carcass structure. The layer may have a uniform thickness, or the layer may have a variable thickness in the axial direction. For example, the layer may have a greater thickness near its outer axial edge relative to the central region (crown).

[0391] Advantageously, the layer or sheet can extend on a surface that substantially corresponds to the extended surface of the belt structure.

[0392] In a preferred embodiment, a layer or sheet of the elastomeric material as described above may be placed between the belt structure and the tire crown, wherein the additional layer or sheet preferably extends on a surface substantially corresponding to the extended surface of the belt structure.

[0393] The elastomeric compound according to the invention can be advantageously incorporated into one or more of the above-described tire components.

[0394] The tire components can be formed by assembling the corresponding semi-finished products on a forming drum (not shown) using at least one assembly device, thereby packaging the tire (100) as described above.

[0395] At least a portion of the components intended to form the tire carcass structure can be constructed and / or assembled on the forming drum. More specifically, the forming drum is adapted to first receive a possible liner and then the tire carcass structure. Subsequently, a device (not shown) engages coaxially about each end flap, and in a position coaxially inclined about the cylindrical tire carcass sleeve, one of the annular anchoring structures arranges an outer sleeve containing the belt structure and the tire crown, and the tire carcass sleeve is shaped into an annular configuration by the radial expansion of the tire carcass structure to determine the radial inner surface of the outer sleeve against which it is applied.

[0396] After packaging the raw tires, molding and vulcanization processes are performed to determine the structural stability of the tires by vulcanizing the elastomer composition and imprinting the desired tread pattern on the crown and any unique graphic markings on the sidewalls.

[0397] Experimental Section

[0398] Analytical methods

[0399] Thermogravimetric analysis (TGA)

[0400] The thermal behavior of 2,5-disubstituted tetrazolium (Table 1) and the functionalized crosslinking agent (I) of this invention (Table 2) was investigated by thermogravimetric analysis using a Mettler Toledo TGA / DSC1 StarE instrument. Approximately 5 mg of pure substance was added to the crucible, and a heating program from 30°C to 500°C was applied under a flow of N2 at a slope of 5°C / min. Specifically, the temperatures at which the thermally unstable groups began to decompose and release nitrogen (TB and / or T-Tetr) were determined. The temperature at which the decomposition of the thermally unstable groups and the release of nitrogen (TB and / or T-Tetr) began was defined as the temperature at which the derivative of the sample weight curve with respect to time became negative at 0.15 and the absolute value became larger.

[0401] NMR Samples are prepared by dissolving 5-10 mg of the compound to be analyzed in 0.6 ml of deuterated solvent (chloroform, DMSO, D2O).

[0402] NMR spectra were recorded using a Bruker AVANCE III HD 400MHz spectrometer. Chemical shifts (δ) are expressed in parts per million (ppm), and coupling constants are given in Hz. Splitting modes are shown below: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad peak.

[0403] IR The IR spectrum was recorded using a Perkin Elmer Spectrum 100 FT-IR spectrometer equipped with a universal ATR sampling accessory. The range was 4000 cm⁻¹. -1Up to 550cm -1 The mid-infrared region is 4cm -1 All spectra were obtained at a high resolution. The reported spectra are the average of 16 scans for each sample, minus the baseline.

[0404] The sample was directly loaded onto the crystal and pressed down with a metal tip. The spectrum was recorded in ATR (attenuated total reflection) mode.

[0405] Measuring the mechanical properties of rubber compounds

[0406] The elastomer material prepared in the examples was vulcanized to obtain samples on which mechanical properties were evaluated.

[0407] Unless otherwise specified, in the mold, in the hydraulic press, at 190°C and 204 kg / cm² 2 The vulcanization process takes about 30 minutes under pressure.

[0408] Static mechanical properties Measurements were taken at 23°C according to ISO 37:2005. Tensile tests were performed on vulcanized dumbbell-shaped straight shaft specimens. Specifically, the tensile strength CR and elongation at break AR% were measured at different elongation levels (10%, 50%, 100%, and 300%, referred to as CA0.1, CA0.5, CA1, and CA3, respectively).

[0409] Using the Instron Model 1341 dynamic device, in the tension-compression mode described herein, measurements were taken under compression. move mechanical properties E' (dynamic elastic modulus), E" (dynamic viscosity modulus), and Tanδ (loss factor). The vulcanized material specimens (190°C for 30 minutes) were cylindrical (length = 25 mm; diameter = 14 mm), subjected to a dynamic sinusoidal stress of + / - 3.5% relative to the preloaded length by compression preloading to 25% of the initial length, and maintained at a fixed temperature of 0°C or 70°C throughout the test at a frequency of 100 Hz. The dynamic mechanical properties are expressed as E' and Tanδ values. The Tanδ value is calculated as the ratio of the dynamic modulus E" / E'.

[0410] At 70℃ and 10Hz frequency, under the % deformation shown in the table, measurements were performed. Shear dynamic mechanical properties G' (shear dynamic elastic modulus), G" (shear dynamic viscosity modulus), Tanδ (loss factor), and δG'.

[0411] The reagents used to prepare the 2,5-disubstituted tetrazolium and cross-linking functionalizing agent (I) were purchased from Fluorochem or Tokyo Chemical Industry and used as is. Chromatographic purification was performed using Merck 9385 silica gel with a pore size of 60 Å (230-400 mesh).

[0412] Abbreviations: AcOEt: Ethyl acetate; AcCN: Acetonitrile; BPTD: 3-[4-bromomethyl)phenyl]-3-(trifluoromethyl)-3H-bisacrylidine; DABCO: 1,4-diazabicyclo[2.2.2]octane or triethylenediamine; DEAD: Diethyl azodicarboxylate; DMF: Dimethylformamide; DMSO: Dimethyl sulfoxide; DPPA: Diphenylphosphine azide, etOH: Ethanol; PPh3: Triphenylphosphine; TMAH: Tetramethylammonium hydroxide; THF: Tetrahydrofuran; TEA: Triethylamine.

[0413] Example 1

[0414] Preparation and Activation Temperature (T-Tetr) of 2,5-Disubstituted Tetrazol

[0415] Prepare 1.1-1.33 2,5-disubstituted tetrazolium as shown in Table 1 below:

[0416] Table 1

[0417]

[0418]

[0419]

[0420] Thermogravimetric analysis was used to evaluate the thermal behavior of these tetrazolium to investigate the effect of substituents at the 2 and 5 positions of the tetrazolium on the activation temperature T-tetr.

[0421] Some of these tetrazolium, including the reactive group Y, particularly tetrazolium 1.13, 1.25, 1.33 and the monosubstituted tetrazolium (VIa) described below, are then used as intermediates for the functionalization crosslinking agents of synthetic formula (I). The 2,5-disubstituted tetrazolium in Table 1 is prepared as described below.

[0422] 1.1 Synthesis of tetrazolium from aldehyde (V) via hydrazone (IV)

[0423] As described in Chem. Commun. (2016), 52, 9426, a tetraazole with an optional substituted aromatic group at the 2-position and an aromatic group at the 5-position is prepared from the corresponding aldehyde (V) by forming an intermediate hydrazone (IV) according to the previously described general synthetic scheme (a1) or (a2).

[0424] Scheme 7 below specifically relates to derivatives where the aromatic groups at positions 2 and 5 are phenyl, but it is similarly applicable to derivatives where the aromatic groups are optionally substituted in other systems (e.g., thiophene or naphthyl):

[0425] Option 7

[0426]

[0427] As reported in the literature, the synthesis involves two steps:

[0428] - Synthesis of hydrazone Dissolve the aromatic aldehyde (1 equivalent) in ethanol. Add toluenesulfonyl hydrazine (1 equivalent) and reflux for 4-5 hours. Then add water and recover the precipitate formed by filtration. The resulting product can be used in the second step without further purification.

[0429] - Synthesis of disubstituted tetrazolium Solution A is obtained by dissolving the solid hydrazone (1 equivalent) obtained in the first step in pyridine. Simultaneously, solution B is prepared by adding a solution of NaNO2 in water (1 equivalent) to a cooled solution of a suitable aromatic amine R-NH2(VIII) (1 equivalent), concentrated HCl, and water / ethanol (1:1). Solution B is added dropwise to solution A, which is cooled in an ice bath, and the mixture is stirred overnight at room temperature at the end of the addition. The reaction mixture containing dilute hydrochloric acid is then neutralized, and the precipitate formed is recovered by filtration. Depending on the type of tetrazolium, the crude product is purified by column chromatography or by crystallization with a suitable solvent, as detailed below.

[0430] As examples, the synthesis and analysis of some of the tetrazolium and related intermediates listed in Table 1 are described in detail below. Unless otherwise specified, the final tetrazolium and corresponding intermediates can be prepared in a similar manner.

[0431] Synthesis of tetrazolium 1.8, 1.9, 1.10, 1.11, 1.12, 1.14, 1.18, 1.28 (The phenyl group is substituted at the 5-position of the tetrazolium, and the other substituents are at the 2-position.)

[0432] According to scheme 8, by forming the corresponding toluenesulfonylhydrazone (IV-a) and reacting it with a suitable amine (VIII) according to the steps described above, tetrazolium 1.8, 1.9, 1.10, 1.11, 1.12, 1.14, 1.18 and 1.28 are synthesized from benzaldehyde (Va) and p-toluenesulfonylhydrazine.

[0433] Option 8

[0434]

[0435] The toluenesulfonylhydrazone intermediate (E)-N'-benzylidene-4-methylbenzenesulfonylhydrazine (IV-a) is a white solid and is used in the next step without further purification.

[0436] FTIR-ATR (cm -1 ): 574, 619, 664, 686, 703, 750, 815, 836, 853, 907, 957, 1022, 1042, 1093, 1107, 1161, 1187, 1227, 1292, 1311, 1326, 1366, 1437, 1452, 1495, 1596, 2284, 2916, 3033, 3225.

[0437] Synthesis of 2-(4-bromophenyl)-5-phenyl-2H-tetrazole (1.18)

[0438] Tetraazole 1.18 was prepared from toluenesulfonylhydrazone intermediate (IV-a) by reaction with 4-bromoaniline (VIII-c), as shown in Scheme 9 below:

[0439] Option 9

[0440]

[0441] The following procedure was followed: In a round-bottom flask, 1.013 g (3.69 mmol) of (E)-N'-benzylidene-4-methylbenzenesulfonylhydrazine (IV-a) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.254 g, 3.69 mmol) was added dropwise to a cooled mixture (0 °C) of 4-bromoaniline (VIII-c) (0.635 g, 3.69 mmol) and concentrated HCl (0.254 g, 11.07 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acidic solution (5% HCl, 200 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography by elution with a hexane:AcOEt mixture (8:2) to obtain a pure product as a red solid (0.72 g, yield: 65%).

[0442] 1 H NMR (400MHz, CDCl3) δ 8.20-8.15 (m, 2H), 8.06-8.00 (m, 2H), 7.67-7.62 (m, 2H), 7.49-7.42 (m, 3H).

[0443] TGA Analysis T-Tetr 170℃. Decomposes before melting.

[0444] Synthesis of 2-(5-phenyl-2H-tetrazol-2-yl)-9H-fluorene-9-one (1.28)

[0445] Tetraazole 1.28 was prepared from toluenesulfonylhydrazone intermediate (IV-a) by reaction with 2-amino-9H-fluorene-9-one (VIII-B), as shown in Scheme 10 below:

[0446] Option 10

[0447]

[0448] The following procedure was followed: In a round-bottom flask, 0.494 g (1.8 mmol) of (E)-N'-benzylidene-4-methylbenzenesulfonylhydrazine (IV-a) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.114 g, 1.8 mmol) was added dropwise to a cooled mixture (0 °C) of 2-amino-9H-fluorene-9-one (VIII-b) (0.342 g, 1.8 mmol) and concentrated HCl (0.197 g, 5.4 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The reaction was allowed to proceed overnight. The mixture was poured into an acidic solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography after elution with a dichloromethane:hexane mixture (8:2) to obtain a pure product as a green solid (0.070 g, yield: 12%).

[0449] 1 H NMR (400MHz, CDCl3) δ8.50 (d, J=2.0Hz, 1H), 8.39 (dd, J=8.1, 2.0Hz, 1H), 8.27 (dd, J=7.5, 2.0Hz, 2H ), 7.75 (dd, J=7.7, 5.5Hz, 2H), 7.64 (d, J=7.4Hz, 1H), 7.60-7.51 (m, 4H), 7.39 (t, J=7.1Hz, 1H).

[0450] TGA Analysis: T-Tetr 195℃. Decomposes before melting.

[0451] Synthesis of tetrazolium 1.13, 1.16, 1.17, 1.19, 1.20 and 1.21 (4-OH-phenyl at the 5-position of the tetrazolium, OH is optionally protected)

[0452] According to scheme 11 below, tetrazolium 1.13, 1.16, 1.17, 1.19, 1.20 and 1.21 are prepared by forming the corresponding toluenesulfonylhydrazone (IV-b) and reacting it with a suitable amine R-NH2 (VIII) according to the steps described above, thereby starting from 4-hydroxybenzaldehyde (Vb) and p-toluenesulfonylhydrazine.

[0453] Option 11

[0454]

[0455] The toluenesulfonylhydrazone intermediate (E)-N'-(4-hydroxybenzyl)-4-methylbenzenesulfonylhydrazine (IV-b) is a light brown solid that is used directly in the next step without further purification.

[0456] Synthesis of 4-(2-phenyl-2H-tetrazole-5-yl)-phenol (1.13)

[0457] According to the method described above, tetrazolium 1.13 was prepared from the toluenesulfonylhydrazone intermediate (IV-b) by reaction with aniline (VIII-a). The crude product was purified by silica gel chromatography using a hexane:AcOEt mixture (8:2) to give a pure product as an orange solid (yield: 53%).

[0458] 1 H-NMR (500MHz, DMSO) δ10.16 (s, 1H), 8.19-8.10 (m, 2H), 8.06-7.97 (m, 2H), 7.75-7.66 (m, 2H), 7.66-7.58 (m, 2H), 7.02-6.92 (m, 1H).

[0459] TGA Analysis T-Tetr 190℃. Decomposes before melting.

[0460] Synthesis of 4-(2-(4-bromophenyl)-2H-tetrazole-5-yl)-phenol (1.19)

[0461] As shown in Scheme 12 below, tetrazolium 1.19 is prepared from toluenesulfonylhydrazone intermediate (IV-b) by reacting with 4-bromoaniline (VIII-c).

[0462] Option 12

[0463]

[0464] The following procedure was followed: In a round-bottom flask, 1.131 g (3.9 mmol) of (E)-N'-(4-hydroxybenzyl)-4-methylbenzenesulfonylhydrazine (IV-b) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.67 g, 3.9 mmol) was added dropwise to a cooled mixture (0 °C) of 4-bromoaniline (VIII-c) (0.269 g, 3.9 mmol) and concentrated HCl (0.426 g, 11.7 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acidic solution (5% HCl, 300 mL), and the precipitate formed was collected by filtration. The crude product was purified by silica gel chromatography by elution with a mixture of hexane and AcOEt (3:2) to obtain a pure product as a light pink solid (0.057 g, yield: 4.7%).

[0465] 1 H NMR (400MHz, CDCl3) δ 8.17-8.12 (m, 2H), 8.10-8.06 (m, 2H), 7.73-7.68 (m, 2H), 7.01-6.95 (m, 2H).

[0466] TGA Analysis: T-Tetr 200℃. Decomposes before melting.

[0467] Synthesis of 2-(3-fluorophenyl)-5-phenyl-2H-tetrazole (1.20)

[0468] As shown in Scheme 13 below, tetrazolium 1.20 is prepared from toluenesulfonylhydrazone intermediate (IV-b) by reacting with 3-fluoroaniline (VIII-d).

[0469] Option 13

[0470]

[0471] The following procedure was followed: In a round-bottom flask, 1.3 g (4.48 mmol) of bis(E)-N'-(4-hydroxybenzyl)-4-methylbenzenesulfonylhydrazine (IV-b) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.309 g, 4.48 mmol) was added dropwise to a cooled mixture (0 °C) of 3-fluoroaniline (VIII-d) (0.498 g, 4.48 mmol) and concentrated HCl (0.490 g, 13.44 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acidic solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography by elution with a mixture of hexane and AcOEt (3:2) to obtain a pure product as a purple solid (0.115 g, yield: 10%).

[0472] 1 H NMR (400MHz, CDCl3) δ 8.20-8.15 (m, 2H), 8.04 (d, J = 8.3Hz, 1H), 7.96 (dt, J = 9.3, 2.2Hz, 1H), 7.61-7.53 (m, 1H), 7.26-7.20 (m, 1H), 7.03-6.98 (m, 2H).

[0473] TGA Analysis T-Tetr 180℃. Decomposes before melting.

[0474] Synthesis of tetrazolium 1.3, 1.4, 1.5, 1.24, 1.25, 1.27 and 1.29 (Thiophene at the 5 position of tetrazolium can be optionally substituted)

[0475] Tetraazoles 1.3, 1.4, 1.5, 1.24, 1.25, 1.27 and 1.29 are prepared by forming toluenesulfonylhydrazine intermediates (IV-c and IV-d) thiophene and reacting them with a suitable amine (VIII) according to the method described above, thereby starting from 2-thiophene-formaldehyde (vc), optionally substituted (Vd) and p-toluenesulfonylhydrazine.

[0476] Synthesis of 2-phenyl-5-(2-thienyl)-2H-tetrazole (1,3)

[0477] Synthesis of i)(E)-4-methyl-N'-(thiophene-2-ylmethylene)benzenesulfonylhydrazine (IV-c)

[0478] The synthesis of the intermediate hydrazone (IV-c) was carried out as described below with respect to tetrazolium 1.24.

[0479] ii) 2-Phenylacetyl-5-(2-thienyl)-2H-tetrazole (1.3) Synthesis

[0480] As shown in Scheme 14 below, tetrazolium 1.3 is prepared from toluenesulfonylhydrazone intermediate (IV-c) by reacting with aniline (VIII-A).

[0481] Option 14

[0482]

[0483] The following procedure was followed: In a round-bottom flask, 2.30 g (8.20 mmol) of (E)-4-methyl-N'-(thiophene-2-ylmethylene)benzenesulfonylhydrazine (IV-C) was dissolved in pyridine (30 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.57 g, 8.20 mmol) was added dropwise to a cooled mixture (0 °C) of aniline (VIII-C) (0.76 g, 8.20 mmol) and concentrated HCl (0.89 g, 24.60 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acid solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography using a 1:1 mixture of hexane and dichloromethane to obtain a pure product as a yellow solid (1.03 g, yield: 55%).

[0484] 1 H NMR (400MHz, CDCl3) δ 8.24-8.18 (m, 2H), 7.94 (dd, J=3.7, 1.2Hz, 1H), 7.64-7.57 (m, 2H), 7.56-7.50 (m, 2H), 7.25-7.20 (m, 1H).

[0485] TGA Analysis T-Tetr 150℃. Decomposes before melting.

[0486] Synthesis of 2-(4-methoxyphenyl)-5-(thiophen-2-yl)-2H-tetrazole (1,24)

[0487] Synthetic scheme 15 for i)(E)-4-methyl-N'-(thiophene-2-ylmethylene)benzenesulfonylhydrazine (IV-c)

[0488]

[0489] 5.00 g (44.6 mmol) thiophene-2-carboxaldehyde (VC), 8.3 g (44.6 mmol) p-toluenesulfonyl hydrazine, and 50 mL EtOH were added to a round-bottom flask equipped with a water condenser. The reaction mixture was heated under reflux for 5 hours with magnetic stirring. The reaction mixture was allowed to cool to room temperature and then poured into cold water. The precipitate formed was collected by filtration to give the desired compound as a pale yellow solid (12.0 g, yield: 96%), which was used directly in the next step without further purification.

[0490] 1 H NMR (400MHz, DMSO) δ11.36 (s, 1H), 8.08 (s, 1H), 7.75-7.70 (m, 2H), 7.59 (dt, J=5.0, 0.9Hz, 1H), 7.41 (d, J=8. 0, 0.9Hz, 1H), 41 (d, J=8.0Hz, 2H), 7.35 (dd, J=3.6, 1.0Hz, 1H), 7.07 (dd, J=5.0, 3.6Hz, 1H), 2.37 (s, 3H).

[0491] ii) Synthetic scheme 16 for 2-(4-methoxyphenyl)-5-(thiophen-2-yl)-2H-tetrazole (1,24)

[0492]

[0493] In a round-bottom flask, (E)-4-methyl-N'-(thiophene-2-ylmethylene)benzenesulfonylhydrazine (IV-c) (2.53 g, 9 mmol) and DABCO (3.03 g, 27 mmol) were dissolved in AcCN (60 mL) to obtain solution A. Simultaneously, anisidine (2.2 g, 18 mmol) and p-toluenesulfonic acid monohydrate (3.4 g, 18 mmol) were dissolved in AcOEt; after 15 minutes, amyl nitrite (4.8 mL, 36 mmol) was added, and the solution was allowed to stir for 15 minutes, collecting solid B. Solid B was filtered and washed with AcOEt. Solution A was cooled to -15 °C with an ice and salt bath, and then solid B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into water, and the precipitate formed was collected by filtration. The crude product was purified by silica gel chromatography by elution with dichloromethane, and the pure product was collected as an orange solid (1.2 g, yield: 51%).

[0494] 1 H NMR(400MHz, CDCl3) δ8.11-8.06 (m, 2H), 7.89 (dd, J=3.6, 1.2Hz, 1H), 7.49 (dd, J= 5.0, 1.1Hz, 1H), 7.19 (dd, J=5.0, 3.7Hz, 1H), 7.09-7.03 (m, 2H), 3.90 (s, 3H).

[0495] TGA Analysis T-Tetr 180℃. Decomposes before melting.

[0496] Synthetic scheme 17 for 4-(5-(thiophen-2-yl)-2H-tetrazole-2-yl)phenol (1,25)

[0497]

[0498] Aluminum chloride (5.0 g, 37.2 mmol) was suspended in dichloromethane and cooled in an ice bath under a nitrogen atmosphere. Trimethylammonium chloride (1.8 g, 18.6 mmol) was then added with stirring. After addition, the suspension was heated to room temperature and stirred for 2 hours. Then, 2-(4-methoxyphenyl)-5-(thiophen-2-yl)-2H-tetrazole (1.2 g, 4.6 mmol) was added to the solution, and the mixture was heated to reflux. The reaction was monitored by TLC. When the reaction was complete, the mixture was poured into 1 M HCl solution. The aqueous layer was extracted three times with AcOEt. The organic phase was washed with saturated NaHCO3 solution and salt solution, then dried over Na2SO4 and the solvent was evaporated. The crude product was purified by silica gel chromatography by elution with dichloromethane, and the pure product was collected as a green solid (1.0 g, yield: 89%).

[0499] 1 H NMR (400MHz, CDCl3) δ 8.07-8.03 (m, 2H), 7.89 (dd, J=3.7, 1.2Hz, 1H), 7.49 (dd, J=5.0, 1.2Hz, 1H), 7.19 (dd, J=5.0, 3.7Hz, 1H), 7.02-6.97 (m, 2H).

[0500] TGA Analysis T-Tetr 190℃. Decomposes before melting.

[0501] Synthesis of [5-(2-phenyl-2H-tetrazol-5-yl)-2-thienyl]boronic acid (1,27)

[0502] Tetraazole 1.27 was prepared according to the following scheme 18:

[0503] Option 18

[0504]

[0505] i) Preparation of hydrazone [5-(2-phenyl-2H-tetrazol-5-yl)-2-thienyl]boronic acid (IV-d)

[0506] 5-Formyl-2-thienylboronic acid (Vd) (1 equivalent) was dissolved in ethanol. Toluenesulfonyl hydrazine (1 equivalent) was added, and the mixture was stirred and refluxed for 4 hours. Water was then added, and the precipitate was recovered by filtration. The product thus obtained (IV-d) could be used in the second step without further purification.

[0507] ii) Convert hydrazone [5-((E)-{[(4-methylphenyl)sulfonyl]hydrazone}methyl)-2-thienyl]boronic acid (IV-d) to [5-(2-phenyl-2H-tetrazole-5-yl)-2-thienyl]boronic acid (1.27)

[0508] - Dissolve the solid (1 equivalent) obtained in step 1 in pyridine to obtain solution A. Meanwhile, prepare solution B by adding an aqueous solution of NaNO2 (1 equivalent) to a cooled solution of aniline (VIII-a) (1 equivalent), concentrated HCl, and water / ethanol (1:1).

[0509] Solution B was slowly added dropwise to solution A, which was cooled in an ice bath, and the mixture was stirred overnight at room temperature at the end of the addition. The reaction mixture containing dilute HCl was then neutralized, and the precipitate formed was recovered by filtration. The crude product was washed with dichloromethane to give a light orange solid.

[0510] 1 H NMR (400MHz, DMSO) δ8.50 (s, 1H), 8.14 (dd, J=8.3, 1.0Hz, 1H), 7.93 (d, J=3.6Hz, 1H), 7.78 (d, J=3.6Hz, 1H), 7.74-7.67 (m, 1H), 7.67-7.61 (m, 1H).

[0511] TGA Analysis Thermogravimetric analysis showed that the weight loss due to nitrogen release began at a temperature of approximately 140°C.

[0512] Synthesis of 2-(5-(thiophen-2-yl)-2H-tetrazol-2-yl)-9H-fluorene-9-one (1.29)

[0513] i) Synthesis of 2-nitro-9H-fluorene-9-one

[0514] Option 19

[0515]

[0516] A mixture of 9H-fluorene-9-one (4.050 g, 22.5 mmol) and H₂O (4 mL) was brought to 80 °C. Then, a mixture of HNO₃ (65%, 4.0 mL, 68.55 mmol) and H₂SO₄ (98%, 4.7 mL, 88.8 mmol) was added dropwise. After stirring at 90 °C for 2.5 hours, the reaction mixture was quenched in water (80 mL). The solid was filtered, washed with water, and dried. TLC showed that the reaction was incomplete. For further purification, the solid was washed back with EtOH (90 mL) for 1 hour. After cooling, the solid was filtered and recrystallized from AcCN (175 mL), collecting the pure product as a yellow solid (3.474 g, yield: 69%).

[0517] 1 H NMR (400MHz, CDCl3) δ8.49 (dd, J=2.2, 0.5Hz, 1H), 8.42 (dd, J=8.2, 2.2Hz, 1H), 7.80-7.76 (m, 1H), 7.71 (dd, J=8 .2, 2.2Hz, 1H), 71 (dd, J=8.2, 0,5Hz, 1H), 7.69-7.66 (m, 1H), 7.61 (td, J=7.5, 1.2Hz, 1H), 7.48-7.44 (m, 1H).

[0518] ii) Synthesis of 2-amino-9H-fluorene-9-one (VIII-b)

[0519] Option 20

[0520]

[0521] Under a nitrogen atmosphere, SnCl₂-2H₂O (12.0 g, 53.29 mmol) was added to a solution of 2-nitro-9H-fluorene-9-one (4.0 g, 17.76 mmol) in AcOEt (44 mL). The mixture was stirred at reflux for 24 hours and then poured onto ice (100 g). The pH of the mixture was adjusted to alkaline (pH 9-10) by adding aqueous NaOH solution, and finally extracted with AcOEt. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed by filtration. The crude product was purified by silica gel chromatography by elution with a dichloromethane:AcOEt mixture (8:2), and the pure product was collected as a deep purple solid (3.0 g, yield: 87%).

[0522] 1 H NMR(400MHz, CDCl3) δ7.58-7.55 (m, 1H), 7.40 (td, J=7.4, 1.2Hz, 1H), 7.36-7.32 (m, 1H), 7.28 (dd, J=7.9, 0.5H z, 1H).9, 0.5Hz, 1H), 7.15 (td, J=7.4, 1.1Hz, 1H), 6.97 (dd, J=2.3, 0.5Hz, 1H), 6.73 (dd, J=7.9, 2.3Hz, 1H).

[0523] iii) Synthesis of 2-(5-(thiophen-2-yl)-2H-tetrazol-2-yl)-9H-fluorene-9-one (1.29)

[0524] As shown in Scheme 21 below, tetrazolium 1.29 is prepared from toluenesulfonylhydrazone intermediate (IV-c) by reacting with 2-amino-9H-fluorene-9-one (VIII-b).

[0525] Option 21

[0526]

[0527] The following procedure was followed: In a round-bottom flask, 0.804 g (2.9 mmol) of (E)-4-methyl-N'-(thiophene-2-ylmethylene)benzenesulfonylhydrazine (IV-c) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, 0.200 g (2.9 mmol) of aqueous NaNO2 solution was added dropwise to a cooled mixture (0 °C) of 2-amino-9H-fluorene-9-one (VIII-b) (0.559 g (2.9 mmol) and concentrated HCl (0.317 g (8.7 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The reaction was allowed to proceed overnight. The mixture was poured into an acid solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography after elution with dichloromethane to obtain a pure product as a red solid (0.090 g, yield: 9%).

[0528] 1 H NMR (400MHz, CDCl3) δ8.48 (d, J=2.0Hz, 1H), 8.36 (dd, J=8.1, 2.0Hz, 1H), 7.94 (dd, J=3.6, 1.0Hz, 1H), 7.74 (t, J= 8.0Hz, 1H).74 (t, J=8.2Hz, 2H), 7.65-7.51 (m, 3H), 7.39 (dd, J=7.4, 6.6Hz, 1H), 7.21 (dd, J=5.0, 3.7Hz, 1H).

[0529] TGA Analysis T-Tetr 185℃. Decomposes before melting.

[0530] Tetraazoles 1.1, 1.2, 1.6, 1.30, 1.31, and 1.32 (Optionally, a substituted phenyl or other aromatic group is substituted at the 5-position of the tetrazolium) Synthesis

[0531] Tetraazoles 1.1, 1.2, 1.6, 1.30, 1.31 and 1.32 are prepared by forming a toluenesulfonyl hydrazine intermediate (IV) and reacting it with a suitable amine (VIII) according to the steps described above, starting with the corresponding optionally substituted formaldehyde (V) and p-toluenesulfonyl hydrazine.

[0532] Synthesis of 4-(2-phenyl-2H-tetrazol-5-yl)-benzoic acid (1.1)

[0533] Synthetic scheme 22 for i)(E)-methyl 4-((2-toluenesulfonylhydrazone)methyl)-benzoate (IV-I)

[0534]

[0535] 1.50 g (9.99 mmol) of 4-formylbenzoic acid (Vi), 1.85 g (9.99 mmol) of p-toluenesulfonyl hydrazine, and 30 mL of EtOH were added to a round-bottom flask equipped with a water condenser. The reaction mixture was heated under reflux for 5 hours with magnetic stirring. The reaction mixture was allowed to cool to room temperature and then poured into cold water. The precipitate formed was collected by filtration to give the desired compound as a white solid (3.12 g, yield: 98%). The product was used directly in the next step without further purification.

[0536] ii) Synthesis of 4-(2-phenyl-2H-tetrazole-5-yl)]-benzoic acid (1.1)

[0537] As shown in Scheme 23 below, tetrazolium 1.1 is prepared from the toluenesulfonylhydrazone intermediate (IV-i) by reacting with aniline (VIII-a) followed by hydrolysis:

[0538] Option 23

[0539]

[0540] The following procedure was followed: In a round-bottom flask, 3.01 g (9.45 mmol) of (E)-methyl-4-((2-toluenesulfonylhydrazone)methyl)-benzoic acid (IV-i) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO₂ (0.65 g, 9.45 mmol) was added dropwise to a cooled mixture (0 °C) of aniline (VIII-a) (0.68 g, 9.45 mmol) and concentrated HCl (1.03 g, 28.35 mmol) dissolved in 10 mL of H₂O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acid solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by washing with methanol, and the pure product was collected as a white solid (1.76 g, yield: 70%).

[0541] 1 H NMR (400MHz, DMSO-d6) δ13.35 (s, 1H), 8.34-8.27 (m, 2H), 8.23-8.13 (m, 4H), 7.73 (tt, J=8.8, 1.8Hz, 2H), 7.70-7.62 (m, 1H).

[0542] TGA Analysis T-Tetr 210℃. Decomposes before melting.

[0543] Synthesis of 4-[4-(2-phenyl-2H-tetrazol-5-yl)phenyl]-1,2,4-triazolidine-3,5-dione (1,2)

[0544] Synthesis of 2-((4-(2-phenyl-2H-tetrazol-5-yl)phenyl)carbamoyl)ethyl 4-i)hydrazinocarbamate (IV-j)

[0545] Option 24

[0546]

[0547] Under a nitrogen atmosphere, 200 mg (0.75 mmol) of tetrazolium 1.1 and 25 mL of anhydrous THF were added to a round-bottom flask equipped with a bubble dropper. The reaction was cooled to 0 °C, and then 230 mg (0.83 mmol) of diphenylphosphoazide (DPPA) was added. After 10 minutes, 80 mg (0.83 mmol) of triethylamine (tea) was added. The reaction was refluxed for 2 hours with magnetic stirring. Subsequently, 70 mg (0.75 mmol) of ethyl hydrazine carbamate was added, and the mixture was refluxed again for 2 hours. After removing the low-pressure solvent, the crude product was extracted three times with AcOEt and washed with NaHCO3 (aqueous solution), H2O, and HCl (1 M). The organic phase was dehydrated, filtered, and evaporated under low pressure to give the intermediate product (209 mg, yield: 76%). The product was used in the next step without further purification.

[0548] ii) Synthesis of 4-[4-(2-phenyl-2H-tetrazol-5-yl)phenyl]-1,2,4-triazolidine-3,5-dione (1.2)

[0549] As shown in Scheme 25 below, tetrazolium 1.2 is prepared from intermediate (IV-j):

[0550] Option 25

[0551]

[0552] The following procedure was followed: 100 mg (0.27 mmol) of 2-((4-(2-phenyl-2H-tetrazol-5-yl)phenyl)carbamoyl)ethyl hydrazinoate and 10 mL of 5 M KOH solution were added to a round-bottom flask equipped with a bubble dropper. The reaction was heated under reflux for 12 hours with magnetic stirring. After cooling, HCl was added to reach pH 2. The precipitate was filtered to give the product as a white solid (86 mg, 99% yield).

[0553] 1 H NMR (400MHz, D2O) δ8.32-8.29 (m, 2H), 8.17-8.13 (m, 1H), 7.70-7.63 (m, 4H), 7.59-7.56 (m, 2H).

[0554] TGA Analysis: T-Tetr 200℃. Decomposes before melting.

[0555] Synthesis of 2-(naphthyl-1-yl)-5-(naphthyl-2-yl)-2H-tetrazole (1,6)

[0556] As shown in Scheme 26 below, tetrazolium 1.6 is prepared from toluenesulfonylhydrazone intermediate (IV-h) by reacting with naphthalene-1-amine (VIII-e).

[0557] Option 26

[0558]

[0559] The following procedure was followed: In a round-bottom flask, 1.034 g (3.2 mmol) of (E)-4-methyl-N'-(naphthyl-2-ylmethylene)benzenesulfonylhydrazine (IV-h) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.220 g, 3.2 mmol) was added dropwise to a cooled mixture (0 °C) of naphthyl-1-amine (VIII-e) (0.458 g, 3.2 mmol) and concentrated HCl (0.350 g, 9.6 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acid solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography by elution with a mixture of dichloromethane and hexane (7:3), and the pure product was collected as a light purple solid (0.696 g, yield: 67%).

[0560] 1 H NMR (400MHz, CDCl3) δ8.86 (s, 1H), 8.38 (dd, J=8.5, 1.7Hz, 1H), 8.17-8.08 (m, 2H), 8.05- 7.99 (m, 3H), 7.99-7.90 (m, 2H), 7.65 (ddd, J=8.5, 5.9, 5.5Hz, 3H), 7.60-7.55 (m, 2H).

[0561] TGA Analysis T-Tetr 100℃. Decomposes before melting.

[0562] Synthesis of 2,5-bis(naphthyl-1-yl)-2H-tetrazole (1.30)

[0563] As shown in Scheme 27 below, tetrazolium 1.30 is prepared from toluenesulfonylhydrazone intermediate (IV-f) by reacting with naphthalene-1-amine (VIII-e).

[0564] Option 27

[0565]

[0566] The following procedure was followed: In a round-bottom flask, 1.775 g (5.46 mmol) of (E)-4-methyl-N'-(naphthyl-1-ylmethylene)benzenesulfonylhydrazine (IV-f) (prepared from 1-formyl-naphthalene (Vf) according to a procedure similar to Scheme 18) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.377 g, 5.46 mmol) was added dropwise to a cooled mixture (0 °C) of naphthyl-1-amine (VIII-e) (0.782 g, 5.46 mmol) and concentrated HCl (0.597 g, 16.38 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acid solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography by elution with a dichloromethane:hexane mixture (9:1), and the pure product was collected as a pale yellow solid (1.32 g, yield: 75%).

[0567] 1 H NMR (400MHz, CDCl3) δ9.11 (d, J=8.6Hz, 1H), 8.48 (dd, J=7.2, 1.1Hz, 1H), 8.19 (dd, J=6.3, 3.5Hz, 1H), 8.12 (d, J=8.3Hz, 1H), 8.07-7.96 (m, 4H), 7.71-7.56 (m, 6H).

[0568] TGA Analysis T-Tetr 145℃. Decomposes before melting.

[0569] 2-Phenylacetazole-5-(2,4,5-trifluorophenyl)-2H-tetrazole Synthesis of (1.31)

[0570] Synthetic scheme 28 for i)(E)-4-methyl-N'-(2,4,5-trifluorobenzyl)benzene-sulfonylhydrazine (IV-e)

[0571]

[0572] 2.816 g (17.6 mmol) of 2,4,5-trifluorobenzaldehyde (Ve), 3.28 g (17.6 mmol) of p-toluenesulfonyl hydrazine, and 60 mL of EtOH were added to a round-bottom flask equipped with a water condenser. The reaction mixture was heated under reflux for 5 hours with magnetic stirring. The reaction mixture was allowed to cool to room temperature and then poured into cold water. The precipitate formed was collected by filtration to give the desired compound (IV-e) as an orange solid (5.604 g, yield: 97%). The product was used for the next step without further purification.

[0573] 1 H NMR (400MHz, CDCl3) δ7.86 (dd, J=6.6, 1.7Hz, 3H), 7.66 (ddd, J=10.5, 8.9, 6.6Hz, 1H), 7.34 (d, J=8.2Hz, 2H), 6.91 (td, J=9.7, 6.3Hz, 1H), 2.43 (s, 3H).

[0574] 19 F NMR (376MHz, CDCl3) δ-122.48 (dd, J=15.3, 4.1Hz), -128.60--128.90 (m), -140.93 (dd, J=20.8, 15.2Hz).

[0575] ii) Synthesis of 2-phenyl-5-(2,4,5-trifluorophenyl)-2H-tetrazole (1.31)

[0576] As shown in Scheme 29 below, tetrazolium 1.31 is prepared from toluenesulfonylhydrazone intermediate (IVe) by reaction with aniline (VIII-a).

[0577] Option 29

[0578]

[0579] The following procedure was followed: In a round-bottom flask, 5.60 g (20.29 mmol) of (E)-4-methyl-N'-(2,4,5-trifluorobenzyl)benzenesulfonylhydrazine (IV-e) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (1.40 g, 20.29 mmol) was added dropwise to a cooled mixture (0 °C) of aniline (VIII-a) (1.89 g, 20.29 mmol) and concentrated HCl (2.22 g, 60.86 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acid solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography by elution with a dichloromethane:hexane mixture (8:2), and the pure product was collected as a red solid (0.430 g, yield: 8%).

[0580] 1 H NMR (400MHz, CDCl3) δ 8.23-8.18 (m, 2H), 8.12-8.04 (m, 1H), 7.60 (tt, J=8.8, 2.0Hz, 2H), 7.57-7.51 (m, 1H), 7.1 (td, J=9.8, 6.4Hz, 1H).

[0581] 19 F NMR (376MHz, CDCl3) δ -111.75 (dd, J=15.3, 5.5Hz), -129.02 (dd, J=21.6, 6.2Hz), -141.24 (dd, J=21.6, 15.6Hz).

[0582] TGA Analysis T-Tetr 165℃. Decomposes before melting.

[0583] 5-(Anthracene-9-yl)-2-phenyl-2H-tetrazole Synthesis of (1.32)

[0584] Synthetic scheme 30 for i)(E)-N'-(anthracite-9-ylmethylene)-4-methylbenzenesulfonylhydrazine (IV-g)

[0585]

[0586] 0.70 g (3.4 mmol) anthracene-9-carboxaldehyde (V g), 0.632 g (3.4 mmol) p-toluenesulfonyl hydrazine, and 60 mL EtOH were added to a round-bottom flask equipped with a water condenser. The reaction mixture was heated under reflux for 5 hours with magnetic stirring. The reaction mixture was allowed to cool to room temperature and then poured into cold water. The precipitate formed was collected by filtration to give the desired compound as a yellow solid (0.805 g, yield: 63%). The product was used for the next step without further purification.

[0587] 1 H NMR (400MHz, CDCl3) δ8.57 (s, 1H), 8.28 (s, 1H), 8.07 (d, J = 8.5Hz, 2H), 7.80-7.76 (m, 2H), 7.58 (dd, J =6.9, 1.7Hz, 3H), 7.55-7.49 (m, 1H), 7.46-7.41 (m, 2H), 7.39 (dd, J=8.8, 4.6Hz, 2H), 2.52 (s, 3H).

[0588] ii) Synthesis of 5-(anthracite-9-yl)-2-phenyl-2H-tetrazole (1,32)

[0589] As shown in Scheme 31 below, tetrazolium 1.32 is prepared from the toluenesulfonylhydrazone intermediate (IV-g) by reaction with aniline (VIII-a):

[0590] Option 31

[0591]

[0592] The following procedure was followed: In a round-bottom flask, 0.303 g (0.8 mmol) of (E)-4-methyl-N'-(2,4,5-trifluorobenzyl)benzenesulfonylhydrazine (IV-g) was dissolved in pyridine (70 mL) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (0.056 g, 0.8 mmol) was added dropwise to a cooled mixture (0 °C) of aniline (VIII-a) (0.075 g, 0.8 mmol) and concentrated HCl (0.088 g, 2.4 mmol) dissolved in 20 mL of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acid solution (5% HCl, 300 mL), and the precipitate formed was collected using a filter funnel. The crude product was purified by silica gel chromatography by elution with dichloromethane, and the pure product was collected as a brown solid (0.027 g, yield: 11%).

[0593] 1 H NMR (400MHz, CDCl3) δ8.66 (s, 1H), 8.35 (dd, J=7.8, 1.7Hz, 2H), 8.09 (dd, J=7.2, 2 .2Hz, 2H), 7.93-7.88 (m, 2H), 7.63 (dd, J=8.4, 7.1Hz, 2H), 7.58-7.45 (m, 5H).

[0594] TGA Analysis T-Tetr 170℃. Decomposes before melting.

[0595] 1.2 Synthesis of tetrazolium (VI) from nitrile (VII) and alkylation

[0596] Alternative routes for the synthesis of 2,5-disubstituted tetrazolium include, according to the synthesis (b1) and (b2) shown above, starting with a suitable nitrile R-CN (VII), preparing a tetrazolium (VI) with a monosubstituted nitrile at the 5-position, and subsequently alkylating it at the 2-position.

[0597] As examples, the synthesis and analysis of some of the tetrazolium and related intermediates listed in Table 1 are detailed below. Regardless of whether specifically described, the final tetrazolium and its respective intermediates can be prepared in a similar manner.

[0598] Synthesis of tetrazolium 1.6, 1.14, 1.15, 1.16, 1.22, 1.23 and 1.26

[0599] According to general schemes 5 and 6 (synthesis of b1 and b2), and more particularly according to schemes 32-38, tetrazolium 1.6, 1.14, 1.15, 1.16, 1.22, 1.23 and 1.26 are prepared by nitrogen alkylation at the 2-position of the 2H-tetrazole intermediate.

[0600] 2-(naphthyl-1-yl)-5-(naphthyl-2-yl)-2H-tetrazole Synthesis of (1.6)

[0601] As shown in Scheme 32 below, tetrazolium 1.6 is prepared by reacting 5-(naphthyl-2-yl)-2H-tetrazole (VI-d) with naphthyl-1-ylboronic acid:

[0602] Option 32

[0603]

[0604] The following steps were performed: 5-(naphthyl-2-yl)-2H-tetrazole (VI-d) (0.3 mmol, 0.059 g), naphthyl-1-ylboronic acid (0.6 mmol, 0.103 g), Cu₂O (0.3 mmol, 0.043 g), and DMSO (4 mL) were added to a 50 mL round-bottom flask. The reaction mixture was stirred at 100 °C until the tetrazolium disappeared as monitored by TLC. The reaction mixture was then cooled to room temperature and diluted with 40 mL of AcOEt, followed by washing with 5 mL of 12 M HCl and 5 mL of salt solution (four times). The organic layer was separated, dried over MgSO₄, and then concentrated under low pressure. The crude product was purified by silica gel chromatography by elution with a hexane:dichloromethane mixture (1:1), and the pure product was collected as a white solid, 1.6 g (0.015 g, yield: 16%).

[0605] 1 H NMR (400MHz, CDCl3) δ8,86 (d, J=0.7Hz, 1H), 8,38 (dd, J=8.5, 1.7Hz, 1H), 8.16-8.13 (m, 1H), 8.11 (dd, J=8.3, 0.8Hz, 1H), 8 .04-7.99 (m, 3H), 7.96 (dd, J=7.4, 1.2Hz, 1H), 7.94-7.90 (m, 1H), 7.65 (ddd, J=5.8, 4.6, 1.8Hz, 3H), 7.59-7.55 (m, 2H).

[0606] TGA Analysis T-Tetr 100℃. Decomposes before melting.

[0607] 2,5-Diphenyl-2H-tetrazole Synthesis of (1.7)

[0608] As shown in Scheme 33 below, tetrazolium 1.7 is prepared by reacting 5-phenyl-2H-tetrazole (VI-a) with 2-phenylboronic acid:

[0609] Option 33

[0610]

[0611] The following steps were performed: 5-Phenyletetrazole (VI-a) (0.51 mmol, 0.074 g), phenylboronic acid (1.12 mmol, 0.137 g), Cu₂O (5 mol%, 0.03 mmol, 0.004 g), and DMSO (4 mL) were added to a 50 mL round-bottom flask. The reaction mixture was stirred at 100 °C until tetrazolium (VI-a) disappeared as monitored by TLC. The reaction mixture was then cooled to room temperature and diluted with 40 mL of AcOEt, followed by washing with 5 mL of 12 M HCl and 5 mL of salt solution (four times). The organic layer was separated, dried over MgSO₄, and then concentrated under low pressure. The crude product was purified by silica gel chromatography by elution with dichloromethane, and the pure product was collected as a white solid, 1.7 g (0.016 g, yield: 14%).

[0612] 1 H NMR (400MHz, CDCl3) δ8.26 (m, 2H), 8.23-8.18 (m, 2H), 7.62-7.49 (m, 6H).

[0613] TGA Analysis: T-Tetr 170℃. Decomposes before melting.

[0614] 2-Benzyl-5-phenyl-2H-tetrazole Synthesis of (1.14)

[0615] Tetraazole 1.14 was prepared according to the following scheme 34:

[0616] Option 34

[0617]

[0618] (i) Synthesis of 5-phenyl-2H-tetrazole (VI-a)

[0619] Benzyl nitrile (1 equivalent) (VII-a) was suspended in H₂O, and ZnBr₂ (1 equivalent) and sodium azide (1.1 equivalent) were added. The mixture was heated under reflux with stirring for 48 hours. The reaction was quenched with HCl (37%) and extracted with ethyl acetate. The organic phase was dehydrated, and the solvent was evaporated under low pressure. The resulting solid was treated with 0.25 M NaOH solution with stirring for 30 minutes. The zinc oxide thus formed was filtered by washing with 1 N NaOH. The resulting aqueous solution was treated with concentrated HCl until acidic pH was reached. The precipitated tetrazolium was recovered, filtered, washed with 3 M HCl, and finally dried in a furnace. Tetrazolium (VI-a) was recovered as a white powder (76% yield).

[0620] ii) Synthesis of 2-benzyl-5-phenyl-2H-tetrazole (1.14)

[0621] Glassware was rinsed under a stream of N2. 5-Phenylacetazole (VI-a) (1 equivalent) was dissolved in anhydrous dimethylformamide, K2CO3 (1.2 equivalents) was added, and benzyl bromide (1 equivalent) was added after 15 minutes. The mixture was magnetically stirred at room temperature for 24 hours. The reaction mixture was extracted with dichloromethane. The organic phase was dehydrated and evaporated under low pressure. The crude product was purified by column chromatography to give 1.14 1-benzyl-5-phenyl-2H-tetrazole as a white solid (90% yield).

[0622] 1 H NMR (400MHz, CDCl3) δ8.16-8.10 (m, 2H), 7.50-7.33 (m, 8H), 5.81 (s, 2H).

[0623] TGA Analysis T-Tetr 200℃. Decomposes before melting.

[0624] 2-Benzyl-5-(thiophen-2-yl)-2H-tetrazole Synthesis of (1.15)

[0625] Tetraazole 1.15 was prepared according to the following scheme 35:

[0626] Option 35

[0627]

[0628] i) Synthesis of 5-(thiophen-2-yl)-2H-tetrazole (VI-b)

[0629] 2-Thiophenonenitrile (VII-b) (1 equivalent) was suspended in H2O, and ZnBr2 (1 equivalent) and sodium azide (1.1 equivalent) were added.

[0630] The mixture was heated under reflux with stirring for 48 hours. The reaction was quenched with HCl (37%) and extracted with ethyl acetate. The organic phase was dehydrated, and the solvent was evaporated under low pressure. The resulting solid was treated with 0.25 M NaOH solution with stirring for 30 minutes. The zinc oxide thus formed was filtered by washing with 1 N NaOH. The resulting aqueous solution was treated with concentrated HCl until an acidic pH was reached. The precipitated tetraazole was recovered, filtered, washed with 3 M HCl, and finally dried in a furnace. Tetraazole (VI-b) was recovered as a white powder (74% yield).

[0631] 1 H NMR (400MHz, DMSO) δ7.93-7.78 (m, 2H), 7.30 (dd, J=5.0, 3.7Hz, 1H).

[0632] ii) Synthesis of 2-benzyl-5-(thiophen-2-yl)-2H-tetrazole 1.15

[0633] The glassware was rinsed under a stream of N2. 5-Thiophenyl-tetrazole (1 equivalent) was dissolved in anhydrous dimethylformamide, K2CO3 (1.2 equivalents) was added, and benzyl bromide (1 equivalent) was added after 15 minutes. The mixture was magnetically stirred for 24 hours at room temperature. The reaction mixture was extracted with dichloromethane. The organic phase was dehydrated and evaporated under low pressure. The crude product was purified by silica gel column chromatography using dichloromethane as eluent to give 2-benzyl-5-(thiophen-2-yl)-tetrazole as a white solid (85% yield).

[0634] 1 H NMR (500MHz, CDCl3) δ7.79 (d, J=2.8Hz, 1H), 7.46-7.34 (m, 6H), 7.13 (dd, J=4.8, 3.8Hz, 1H), 5.78 (s, 2H).

[0635] TGA Analysis T-Tetr 210℃. Decomposes before melting.

[0636] 5-Phenyl-2-(thiophen-2-yl)-2H-tetrazole Synthesis of (1.22)

[0637] As shown in Scheme 36 below, tetrazolium 1.22 is prepared by reacting 5-phenyl-2H-tetrazole (VI-a) with thiophene-2-ylboronic acid:

[0638] Option 36

[0639]

[0640] The following steps were performed: 5-Phenyletetrazole (VI-a) (0.83 mmol, 0.121 g), thiophene-2-ylboronic acid (1.66 mmol, 0.212 g), Cu₂O (0.83 mmol, 0.119 g), and DMSO (4 mL) were added to a 50 mL round-bottom flask. The reaction mixture was stirred at 100 °C until tetrazolium (VI-a) disappeared as monitored by TLC. The reaction mixture was then cooled to room temperature and diluted with 40 mL of AcOEt, followed by washing with 5 mL of 12 M HCl and 5 mL of salt solution (four times). The organic layer was separated, dried over MgSO₄, and then concentrated under low pressure. The crude product was purified by silica gel chromatography by elution with dichloromethane, and the pure product was collected as a white solid, 1.22 g (0.033 g, yield: 17%).

[0641] 1 H NMR(400MHz, CDCl3) δ8.26-8.20 (m, 2H), 7.70 (dd, J=3.8, 1.4Hz, 1H), 7.52 (dd, J=5.2, 2.0Hz, 3H), 7.30 (dd, J=5.4, 1.4Hz, 1H), 7.10 (dd, J=5.4, 3.9Hz, 1H).

[0642] TGA Analysis T-Tetr 150℃. Decomposes before melting.

[0643] 2,5-Diphenyl-2H-tetrazole Synthesis of (1.23)

[0644] Similar to the scheme described above for tetrazolium 1.15, tetrazolium 1.23 is prepared according to the following scheme 37:

[0645] Option 37

[0646]

[0647] The intermediate 5-benzyl-2H-tetrazole (VI-c) is a white solid.

[0648] 1 H NMR (400MHz, DMSO) δ7.32 (ddd, J=23.2, 7.3, 5.3Hz, 5H), 4.29 (s, 2H).

[0649] The final 2,5-dibenzyl-2H-tetrazole 1.23 was a white solid.

[0650] 1 H NMR (400MHz, CDCl3) δ7.31-7.15(m, 6H), 7.04-6.91(m, 4H), 5.24(s, 2H), 4.08(s, 2H).

[0651] TGA Analysis T-Tetr 220℃. Decomposes before melting.

[0652] 2-Benzyl-5-(naphth-2-yl)-2H-tetrazole Synthesis of (1.26)

[0653] Tetraazole 1.26 was prepared according to the following scheme 38:

[0654] Option 38

[0655]

[0656] i) Synthesis of 5-(naphthyl-2-yl)-2H-tetrazole (VI-d)

[0657] Naphthalene-2-carboxynitrile (VII-d) (1 equivalent) was suspended in H₂O, and ZnBr₂ (1 equivalent) and sodium azide (1.1 equivalent) were added. The mixture was heated under reflux with stirring for 48 hours. The reaction was quenched with HCl (37%) and extracted with ethyl acetate. The organic phase was dehydrated, and the solvent was evaporated under low pressure. The resulting solid was treated with 0.25 M NaOH solution with stirring for 30 minutes. The zinc oxide thus formed was filtered by washing with 1 N NaOH. The resulting aqueous solution was treated with concentrated HCl until an acidic pH was reached. The precipitated tetrazolium was recovered, filtered, washed with 3 M HCl, and finally dried in a furnace. 5-Naphthalene-2-yl-tetraazole (Vi-d) was given as a white powder (41% yield).

[0658] ii) Synthesis of 2-benzyl-5-(naphthyl-2-yl)-2H-tetrazole (1,26)

[0659] Rinse the glassware under a stream of N2. Dissolve 5-naphthyl-tetrazole (VI-d) (1 equivalent) in anhydrous acetonitrile, add K2CO3 (10 equivalents), and after 15 minutes add benzyl bromide (1 equivalent). Stir magnetically for 24 hours at room temperature.

[0660] The reaction mixture was extracted with dichloromethane. The organic phase was dehydrated and evaporated under low pressure. The crude product was purified by column chromatography to give 2-benzyl-5-(naphthyl-2-yl)-2H-tetrazole (1.26), a white solid (yield 38%).

[0661] 1 H NMR (400MHz, CDCl3) δ: 8,68 (s, 1H), 8,21 (d, 1H), 7,94 (d, 2H), 7,53 (m, 2H), 7,46 (d, 2H), 7,42-7,37 (dd, 4H), 5,85 (s, 2H).

[0662] TGA Analysis T-Tetr 210℃. Decomposes before melting.

[0663] Synthesis of tetrazolium 1.33 (The tetrazolium has a 3-OH-phenyl group at the 5-position)

[0664] According to scheme 39 below, tetrazolium 1.33 is prepared by starting with 3-hydroxybenzaldehyde (Vk) and p-toluenesulfonylhydrazine, forming the corresponding toluenesulfonylhydrazone (IV-k), and then converting it to tetrazolium by reacting it with a suitable amine R-NH2 (VIII) according to the steps described below:

[0665] Option 39

[0666]

[0667] The toluenesulfonylhydrazone intermediate (E)-N'-(3-hydroxybenzyl)-4-methylbenzenesulfonylhydrazine (IV-k) is a light brown solid and is used in the next step without further purification.

[0668] 3-[2-(3,5-dichlorophenyl)-2H-tetrazole-5-yl]phenol Synthesis of (1.33)

[0669] As shown in Scheme 40 below, tetrazolium 1.33 is prepared from the toluenesulfonylhydrazone intermediate (IV-k) by reaction with 3,5-dichloroaniline (VIII-f):

[0670] Option 40

[0671]

[0672] The following procedure was followed: In a round-bottom flask, 5.00 g (17.22 mmol) of (E)-N'-(3-hydroxybenzyl)-4-methylbenzenesulfonylhydrazine (IV-k) was dissolved in pyridine (150 ml) to obtain solution A. Simultaneously, an aqueous solution of NaNO2 (1.20 g, 17.22 mmol) was added dropwise to a cooled mixture (0 °C) of 3,5-dichloroaniline (VIII-f) (2.79 g, 17.22 mmol) and concentrated HCl (2.00 g, 51.66 mmol) dissolved in 30 ml of H2O / EtOH (1:1) to obtain solution B. Solution A was cooled in an ice bath, and then solution B was slowly added. The resulting mixture was allowed to react overnight. The mixture was poured into an acid solution (5% HCl, 500 ml), and the precipitate formed was collected by filtration. The crude product was purified by silica gel chromatography by elution with a hexane:AcOEt mixture (3:2), and the pure product was collected as a light orange solid (2.17 g, yield: 41%).

[0673] 1 H NMR (400MHz, CDCl3) δ8.15 (d, J=1.8Hz, 1H), 7.85-7.79 (m, 1H), 7.73 (dd, J=2.5, 1.5Hz, 1H), 7. 50 (t, J=1.8Hz, 1H), 7.42 (t, J=7.9Hz, 1H), 7.01 (ddd, J=8.2, 2.6, 1.0Hz, 1H), 5.07 (s, 1H).

[0674] TGA Analysis: T-Tetr 170℃. Decomposes before melting.

[0675] Thermogravimetric analysis showed that tetrazolium content was 1.1-1.33%.

[0676] Thermogravimetric analysis was performed on the 2,5-disubstituted tetrazolium shown in Table 1 according to the method described above.

[0677] Figure 2 The graphs obtained from TGA for tetrazolium 1.1 and 1.3 are shown. As observed, tetrazolium 1.1 shows a significant increase at around 210 °C as the tetrazolium ring decomposes and releases nitrogen gas. Tetrazolium 1.3, on the other hand, exhibits a more gradual decomposition starting from about 150 °C.

[0678] As shown in Table 1, the activation temperatures T-Tetr of these derivatives range from 100 °C to 250 °C and are influenced by the properties of the substituents present at positions 2 and 5.

[0679] In particular, it has been observed that if an electron-withdrawing group EW, such as a carboxyl group or a triazolidinedione (tetrazole 1.1 and 1.2), is present at the 5-position of the tetrazolium ring, at the para-position of the carbon-bonded phenyl group, the electron-withdrawing group EW stabilizes the tetrazolium by increasing the activation temperature T-Tetr, while an electron-donating group ED, such as thiophene optionally substituted with an amino group (tetrazole 1.3 and 1.5), has the opposite effect when bonded to the carbon of the tetrazolium ring.

[0680] The activation temperatures T-Tetr values ​​reported in Table 1 indicate that tetraazoles with activation temperatures T-Tetr encompassing a wide range of technology-dependent temperatures can be synthesized. Therefore, appropriate combination of substituents on the tetraazole allows the activation temperature T-Tetr of the system to be adapted to the desired application.

[0681] Example 2: Reactivity test of tetrazolium and carbene functional groups

[0682] Example 2A Reactivity and stability tests of 2,5-disubstituted tetrazolium

[0683] To verify the stability and reactivity of 2,5-disubstituted tetrazolium to the more reactive double bonds in polymers, represented by terminal vinyl groups, cycloaddition tests of some tetrazolium in Table 1 were performed using oligomers under different heating conditions as described in Examples 2A1-2A3 below, as shown in Scheme 41 below:

[0684] Option 41

[0685]

[0686] To test the polymer functionalization reaction, using 130 (purchased from Evonik), a stereoselective oligomer of polybutadiene, illustrated below:

[0687]

[0688] Its average molar mass is 4600 g / mol, including:

[0689] - Approximately 77% of the 1,4-double bonds (p)

[0690] - Approximately 22% of 1,4-trans double bonds (n)

[0691] - Approximately 1% of 1,2-vinyl double bonds (m)

[0692] This polymer has a low vinyl content (approximately 1%), which allows for qualitative assessment of the selectivity of the chosen reaction. Furthermore, being a liquid, it is easily mixed, even without the use of a solvent.

[0693] Example 2A1 : Mix tetrazolium derivative 1.1 and 1.2 in a glass tube without solvent. 130 oligomer (molar ratio of tetrazolium / polymer is 1:100, molar ratio of tetrazolium / vinyl polymer groups is 1:1), and the mixture is heated at the tetrazolium activation temperature T-Tetr for 15-30 minutes.

[0694] The formation of pyrazoline by cycloaddition was detected by fluorescence of the sample under UV light (365 nm) and confirmed by IR and NMR spectra measured at the end of the reaction on the modified oligomer after precipitation in ethanol and reaction with tetrazolium. The oligomer was then suspended in ethanol and centrifuged (repeated 3 times) to remove unreacted tetrazolium and byproducts.

[0695] Figure 3 The image shows measurements taken using a Perkin-Elmer Spectrometer 100 (FT-IR) device. 130 ( Figure 3 A) and tetrazolium 1.1 and The reaction products between 130 and 130 ( Figure 3 B) IR spectrum.

[0696] - Figure 4 Showing 130 before the cycloaddition reaction with tetrazolium 1.1 ( Figure 4 A) and afterwards ( Figure 4 B) H-NMR spectrum.

[0697] The 1H-NMR spectrum after the reaction ( Figure 4 In B), with A new signal was observed compared to the 130 signal, which is attributed to the formation of pyrazoline, particularly the signal around 9.5 ppm (carboxyl proton), the signal between 8.5 and 8.0 ppm (phenyl proton), and the signal around 4 ppm (pyrazoline cyclic proton).

[0698] The tests and analyses performed in this embodiment showed that the tetrazolium had decomposed, and the nitrile imine and The double bond reaction at 130 yields the corresponding pyrazole, thereby functionalizing the oligomer.

[0699] Example 2A2 : The pre-selected tetrazolium and 130 oligomers were mixed in vials and heated to 70°C to improve their flowability and better disperse the tetraazole. A portion of the mixture was then placed in the crucible of a thermogravimetric analyzer. The mixture was heated from 30°C to 500°C at a heating gradient of 5°C / min. It was observed that the tetraazole decomposed only upon reaching and exceeding its respective activation temperature T-Tetr.

[0700] Example 2A3 : In TGA Another heating mode for the 130-tetraazole 1.3 mixture, which reproduces the thermal steps that the elastomer mixture typically undergoes under normal production conditions, is used to evaluate the stability of tetraazole at temperatures below the activation temperature T-Tetr, and its activation reaching and exceeding that temperature.

[0701] The procedure comprises, in sequence: a first heating at 140°C for 30 minutes, corresponding to the initial mixing step in the absence of tetrazolium; cooling to 40°C; heating to 90°C for 30 minutes, corresponding to the productive step of incorporating tetrazolium into the mixture; a second cooling to 30°C; and a final heating to simulate the reaction conditions of tetrazolium, wherein the temperature is increased to at least 20°C above the activation temperature T-Tetr. Figure 5 The thermograms show a rapid decrease in the weight of samples including tetrazolium 1.3 at temperatures higher than its activation temperature T-Tetr (150 °C).

[0702] As the only weight loss detectable in the TGA indicates, tetrazolium 1.3 was observed to remain unaffected throughout the rubber compound processing thermal cycle, and it was only activated when the activation temperature T-Tetr was reached and exceeded.

[0703] Example 2B Reactivity test of carbene functional groups

[0704] Several milligrams of commercially available 3-[4-(bromomethyl)phenyl]-3-(trifluoromethyl)-3H-bisacrylidine (III-a) (BPTD) were uniformly dispersed in a 1:1 molar ratio to vinyl groups. 130 °C. The mixture was then heated to the bisacrylamide activation temperature (approximately 100 °C TB) for 30 minutes to obtain carbene. During the reaction, the development of nitrogen bubbles was observed, confirming thermal activation. The reaction scheme related to polymer functionalization is reported below:

[0705] Option 42

[0706]

[0707] At the end of the reaction, the polymer was purified to remove unreacted BPTD by dissolving it in a small amount of dichloromethane, precipitating it in methanol, and centrifuging it. The purified polymer was characterized using NMR to demonstrate the actual functionalization.

[0708] like Figure 6 The NMR spectrum shows an aromatic peak in the region between 7.39 and 7.31 ppm, which can be attributed to the aromatic ring of BPTD. On the other hand, the area of ​​the vinyl double bond of the polymer at 4.99 ppm is slightly different from that of the uncontaminated polymer, presumably these bonds are more likely to react with functionalizing agents. Furthermore, the aliphatic carbon of CH2Br appears at 4.48 ppm, indicating a reaction with BTDP.

[0709] Example 3

[0710] Synthesis of Functionalized Crosslinking Agent (I)

[0711] The functionalized crosslinking reagents of formula (I) containing B-group carbene precursors (3.1-3.3) or azibene precursors (3.4-3.6) were synthesized and characterized as shown in Table 2 below:

[0712] Table 2 Formula (I) Reagent

[0713]

[0714]

[0715] The reported activation temperatures TB and T-Tetr are when contained in The samples of the dispersed reagent of formula (I) observed to begin weight loss in thermogravimetric analysis (TGA) at which point the weight loss was observed. The two activation temperatures of reagent (I) and its solubility in the elastomeric matrix can be specifically altered by selecting appropriate substituents.

[0716] Through alkylation Synthesis of 2-phenyl-5-(4-((4-(3-trifluorophenyl-3H-bisacryl-3-yl)-benzyl)oxy (B-)phenyl)-2H-tetrazole (3.1)

[0717] As generally shown in Scheme 2 and specifically as shown in Scheme 43 herein, cross-linking functionalizing agent 3.1 is prepared starting from tetrazolium intermediate 1.13.

[0718] Option 43

[0719]

[0720] Alkylation with BPTD(III-a) was performed according to the following procedure: 4-(2-phenyl-2H-tetrazole-5-yl)phenol (1.13 g, 0.734 g, 3.1 mmol), K₂CO₃ (4.284 g, 31 mmol), and 100 mL of AcCN were added to a round-bottom flask under an inert and anhydrous atmosphere. After 15 minutes, commercially available BPTD(III-a) (0.5 mL, 3.1 mmol) was added, and the mixture was allowed to stir overnight at room temperature. The mixture was poured into water (300 mL) and extracted with dichloromethane (2 × 20 mL), washed with brine (2 × 10 mL). The organic layer was dried over Na₂SO₄, filtered, and evaporated under low pressure. The crude product was purified by silica gel chromatography by elution with a dichloromethane:hexane mixture (7:3), and the pure product was collected as a white solid, 3.1 g (0.913 g, yield: 72%).

[0721] 1 H-NMR (400MHz, CDCl3) δ 8.21-8.17 (m, 4H), 7.60-7.55 (m, 2H), 7.50 (tt, J=5.9, 1.2Hz, 3H), 7.24 (d, J=8.1Hz, 2H), 7.11-7.07 (m, 2H), 5.16 (s, 2H).

[0722] FTIR-ATR (cm -1 ): 578, 609, 633, 681, 694, 706, 736, 757, 809, 820, 837, 857, 872, 919, 939, 992, 1007, 1018, 1037, 1052, 1076, 1112, 1150, 1171, 1194, 1239, 1305, 1321, 1343, 1389, 1426, 1456, 1462, 1474, 1498, 1520, 1542, 1586, 1598, 1614, 1912, 2059, 2195, 2354, 2922, 3061.

[0723] TGA Analysis TB: 110℃ and T-Tetr: 175℃. Figure 7 TGA analysis of the starting products (bisacrylidine and tetrazolium) and the final product 3.1 is shown. A weight loss of approximately 120°C corresponding to the nitrogen loss of the bisacrylidine fraction and a second weight loss of approximately 190°C corresponding to the nitrogen loss of the tetrazolium fraction can be observed in the final product.

[0724] via Mitsunobu Synthesis of 2-phenyl-5-(4-((4-(3-(trifluorophenyl)-3H-bisacryl-3-yl)-benzyl 2H-tetrazole (3.1)

[0725] Typically, as shown in Scheme 2, and specifically in this document as shown in Scheme 44, the cross-linking functionalizing agent 3.1 is prepared starting from tetrazolium intermediate 1.13.

[0726] Option 44

[0727]

[0728] The reaction with 4-(3-trifluorophenyl-3H-bisacrylidine-3-yl)-phenyl-methanol (III-b) was carried out according to the following procedure via Mitsunobu reaction: Commercially available 4-(2-phenyl-2H-tetrazole-5-yl)phenol (1.13) (0.500 g, 2.1 mmol), 4-(3-trifluorophenyl-3H-bisacrylidine-3-yl)-phenyl-methanol (III-b, 0.302 g, 1.4 mmol), PPh3 (0.734 g, 2.8 mmol), and 20 mL of dichloromethane were added to a round-bottom flask. The mixture was cooled to 0 °C, and then diethyl azodicarbonate (DEAD, 0.488 g, 2.8 mmol) was added in portions. The reaction was stirred overnight at room temperature. The mixture was concentrated under low pressure and eluted with a dichloromethane / hexane mixture (7:3). The product was purified by silica gel chromatography and collected as a white solid 3.1 g (0.531 g, yield: 87%).

[0729] 1 H-NMR (400MHz, CDCl3) δ 8.21-8.17 (m, 4H), 7.60-7.55 (m, 2H), 7.50 (tt, J=5.9, 1.2Hz, 3H), 7.24 (d, J=8.1Hz, 2H), 7.11-7.07 (m, 2H), 5.16 (s, 2H).

[0730] FTIR-ATR (cm -1 ):578,609,633,681,694,706,736,757,809,820,837,857,872,919,939,992,1007,1018,1037,1052,1076,1112,1150,1171,1194,1239,1305,1321,1343,1389,1426,1456,1462,1474,1498,1520,1542,1586,1598,1614,1912,2059,2195,2354,2922,3061.

[0731] TGA Analysis TB 110℃; T-Tetr 175℃. Decomposes before melting.

[0732] Through alkylation Synthesis of 5-phenyl-2-(4-(3-trifluorophenyl-3H-bisacryl-3-yl)benzyl)-2H-tetrazole (3.2)

[0733] Crosslinking functionalizing agent 3.2 is typically prepared from 5-phenyl-2H-tetrazole (VI-a), as shown in Scheme 6 (Synthesis b2) and specifically in this document as Scheme 45.

[0734] Option 45

[0735]

[0736] Alkylation with BPTD(III-) was performed according to the following procedure: 5-phenyl-2H-tetrazole (VI-a) (0.036 g, 0.25 mmol), K₂CO₃ (0.346 g, 2.5 mmol), and 10 mL of AcCN were added to a round-bottom flask under an inert and anhydrous atmosphere. After 15 minutes, commercially available BPTD(III-a) (0.04 mL, 0.25 mmol) was added. The reaction was carried out overnight at room temperature. The mixture was poured into water (300 mL) and extracted with AcOEt (2 x 20 mL), washed with brine (2 x 10 mL). The organic layer was dried over Na₂SO₄, filtered, and evaporated under low pressure. The crude product was purified by silica gel chromatography using dichloromethane as elution, and the pure product was collected as a white solid, 3.2 g (0.057 g, yield: 66%).

[0737] 1 H NMR (400MHz, CDCl3) δ 8.17-8.13 (m, 2H), 7.53-7.47 (m, 5H), 7.24 (d, J=8.1Hz, 2H), 5.84 (s, 2H).

[0738] FTIR-ATR (cm -1 ): 581, 612, 635, 682, 697, 702, 739, 760, 808, 838, 856, 874, 922, 941, 993, 1007, 1018, 1034, 1051, 1112, 1150, 1172, 1193, 1240, 1321, 1345, 1388, 1426, 1464, 1499, 1520, 1545, 1588, 1911, 2062, 2196, 2355, 2924, 3060.

[0739] TGA Analysis TB 110℃; T-Tetr 190℃. Decomposition occurs before melting.

[0740] via Mitsunobu Synthesis of 5-(thiophen-2-yl)-2-(4-((4-(3-trifluorophenyl-3H-bisacryl-3-yl)) Benzyl)oxy)phenyl)-2H-tetrazole (3.3)

[0741] As shown in Scheme 46, cross-linking functionalizing agent 3.3 is prepared starting from 4-(5-(thiophen-2-yl)-2H-tetrazole-2-yl)phenol (1.25):

[0742] Option 46

[0743]

[0744] The Mitsunobu reaction was carried out with (4-(3-trifluorophenyl-3H-bisacrylidin-3-yl)phenyl)methanol(III) according to the following procedure: Commercially available 4-(5-(thiophene-2-yl)-2H-tetrazole-2-yl)phenol (1.25 g) (0.403 g, 1.65 mmol), 4-(3-trifluorophenyl-3H-bisacrylidin-3-yl)-phenyl-methanol(III-b) (0.238 g, 1.1 mmol), PPh3 (0.577 g, 2.2 mmol), and 20 mL of dichloromethane were added to a round-bottom flask. The mixture was cooled to 0 °C, and then DEAD (0.950 g, 2.2 mmol) was added in portions. The reaction was stirred overnight at room temperature. The mixture was concentrated under low pressure the next day and eluted with dichloromethane. It was purified by silica gel chromatography, and the pure product was collected as a pale yellow solid 3.3 (0.445 g, yield: 91%).

[0745] 1 H NMR (400MHz, CDCl3) δ8.08 (t, J=9.1Hz, 3H), 7.89 (dd, J=3.6, 1.2Hz, 1H), 7.52-7.47 (m, 3H) , 7.18 (dd, J=5.0, 3.7Hz, 1H), 7.10 (d, J=9.1Hz, 2H), 7.04 (d, J=9.1Hz, 1H), 5.16 (s, 2H).

[0746] FTIR-ATR (cm -1 ): 576, 613, 686, 710, 735, 750, 812, 834, 852, 938, 966, 1002, 1011, 1031, 1112, 1148, 1240, 1302, 1345, 1384, 1456, 1477, 1512, 1565, 1608, 1654, 1778, 1946, 1971, 2006, 2021, 2049, 2064, 2122, 2142, 2169, 2207, 2932, 3090.

[0747] TGA Analysis TB 130℃; T-Tetr 190℃. Decomposes before melting.

[0748] Synthesis of 5-(2-thienyl)-2-(4-{[4-(2,5-triaz-1-en-2-yn-1-yl-sulfonyl)benzyl]oxy} phenyl)-2H-tetrazole (3.4)

[0749] As generally shown in Scheme 2, and specifically as shown in Scheme 47 below, the cross-linking functionalizing agent 3.4 is prepared by alkylating tetrazolium intermediate 1.25:

[0750] Option 47

[0751]

[0752] Alkylation was performed according to the following procedure: In a round-bottom flask under nitrogen, 1.25 g (1.30 g, 5.30 mmol) of 4-(5-(thiophen-2-yl)-2H-tetrazole-2-yl)phenol was dissolved in 25 mL of anhydrous DMF. 0.88 g (6.36 mmol) of K₂CO₃ was added, followed by 1.47 g (5.30 mmol) of 1-{[4-(bromomethyl)phenyl]sulfonyl}-azide (III-c) after 15 minutes. The reaction was carried out at room temperature for 48 hours. The mixture was poured into water (100 mL) and extracted with AcOEt (3 x 20 mL), washed with brine (3 x 10 mL). The organic phase was dried over Na₂SO₄, filtered, and evaporated under low pressure. The crude product was purified by silica gel chromatography using a mixture of dichloromethane and AcOEt (3:2 ratio) to give a pure product as a pink solid, 3.4 g (1.72 g, yield: 74%).

[0753] 1H NMR (400MHz, CDCl3) δ 8.23-8.04 (m, 2H), 7.91 (ddd, J=21.5, 19.5, 8.4Hz, 3H), 7.63-7.46 (m, 3H), 7.23-7.16 (m, 3H), 4.51 (s, 2H).

[0754] TGA Analysis TB 130℃; T-Tetr 190℃. Decomposes before melting.

[0755] 2-(3,5-Dichlorophenyl)-5-(3-{[4-(2,5-triazine-1-en-2-yn-1-yl-sulfonyl)benzyl]oxy} Synthesis of phenyl)-2H-tetrazole (3,5)

[0756] As generally shown in Scheme 2 and specifically in Scheme 48 below, cross-linking functionalizing agent 3.5 is prepared by alkylation of tetrazolium intermediate 1.33:

[0757] Option 48

[0758]

[0759] Alkylation was performed according to the following procedure: 3-[2-(3,5-dichlorophenyl)-2H-tetrazole-5-yl]phenol (1.33g) (3.00g, 9.77mmol) was dissolved in 30mL of anhydrous DMF in a round-bottom flask under nitrogen atmosphere. K₂CO₃ (1.62g, 11.72mmol) was added, followed by 1-{[4-(bromomethyl)phenyl]sulfonyl}-azide (III-c) (2.70g, 9.77mmol) after 15 minutes. The reaction was carried out at room temperature for 48 hours. The mixture was poured into water (100mL) and extracted with AcOEt (3 × 20mL), washed with salt solution (3 × 10mL). The organic phase was dried over Na₂SO₄, filtered, and evaporated under low pressure. The crude product was purified by silica gel chromatography using a mixture of dichloromethane and AcOEt (3:2 ratio) to give a pure product as a pink solid, 3.5g (3.00g, yield: 61%).

[0760] 1 H NMR( 400MHz, CDCl3) δ 8.19-8.15 (m, 1H), 8.13 (d, J = 1.8Hz, 2H), 7.94-7.89 (m, 2H), 7.89-7.85 (m , 1H), 7.52-7.50 (m, 2H), 7.50-7.46 (m, 2H), 7.17 (ddd, J=8.2, 2.4, 1.0Hz, 1H), 4.49 (s, 2H).

[0761] TGA Analysis ( Figure 9 ): TB 130℃; T-Tetr 170℃. Decomposes before melting.

[0762] 2-(3,5-Dichlorophenyl)-5-(3-{[9-(triaza-1-en-2-yn-1-yl)nonyl]oxy}phenyl)-2H-tetrachlorophenyl Synthesis of azole (3.6)

[0763] As generally shown in Scheme 2 and Schemes 49 and 50 of this paper, the cross-linking functionalizing agent 3.6 is prepared by the Mitsunobu reaction of the tetrazolium intermediate 1.33 and subsequent nucleophilic substitution.

[0764] Option 49

[0765]

[0766] The Mitsunobu reaction with 9-bromononanol was carried out according to the following procedure: Commercially available 3-[2-(3,5-dichlorophenyl)-2H-tetrazole-5-yl]phenol (1.33 g) (0.200 g, 0.65 mmol), 9-bromononanol (0.145 g, 0.65 mmol), PPh3 (0.341 g, 1.3 mmol), and 10 mL of dichloromethane were added to a round-bottom flask. The mixture was cooled to 0 °C, and then DEAD (0.226 g, 1.3 mmol) was added in portions. The reaction was stirred overnight at room temperature. The next day, the mixture was concentrated under low pressure and eluted with a dichloromethane / heptane mixture (1:1), purified by silica gel chromatography, and the pure product was collected as a pale yellow solid (0.100 g, yield: 30%).

[0767] 1 H NMR (400MHz, CDCl3) δ8.14 (d, J=1.8Hz, 2H), 7.82-7.78 (m, 1H), 7.74 (dd, J=2.4, 1.5Hz, 1H), 7.47 (t, J=1.8Hz, 1H), 7.41 (t, J=8.0Hz, 1H), 7.04 (ddd, J=8.3 , 2.6, 0.9Hz, 1H), 4.06 (t, J=6.5Hz, 2H), 3.45-3.38 (m, 2H), 1.92-1.79 (m, 2 H), 1.56-1.47 (m, J=10.5, 5.0Hz, 2H), 1.47-1.39 (m, 2H), 1.39-1.27 (m, 8H).

[0768] Option 50

[0769]

[0770] 5-{3-[(9-bromononyl)oxy]phenyl}-2-(3,5-dichlorophenyl)-2H-tetrazole (0.100 g, 0.195 mmol) and sodium azide (0.026 g, 0.390 mmol) were dissolved in 3 mL of a DMF / H₂O mixture (9:1). The reaction was heated to 80 °C for 22 hours. The mixture was extracted with ethyl acetate, the organic phase was dehydrated, filtered, and evaporated under low pressure to give the pure product (0.092 g, yield: 99%).

[0771] 1 H NMR(400MHz, CDCl3) δ8.14 (d, J=1.8Hz, 2H), 7.84-7.77 (m, 1H), 7.74 (dd, J=2.4, 1.5Hz, 1H), 7.48 (t, J=1.8Hz, 1H), 7.41 (t, J=8.0Hz, 1H), 7.04 (ddd, J=8.3 , 2.6, 0.9Hz, 1H), 4.06 (t, J=6.5Hz, 2H), 3.25 (t, J=7.0Hz, 2H), 1.87-1.78 ( m, 2H), 1.59 (dd, J=14.1, 6.8Hz, 2H), 1.54-1.46 (m, 2H), 1.41-1.27 (m, 8H).

[0772] Example 4

[0773] Preparation of elastomer compounds containing carbene crosslinking functionalizing agent (I)

[0774] Comparative elastomer compounds (e.g., 4.1 without the formula (I) reagent, thus having an unmodified SBR) and elastomer compounds according to the invention (Examples 4.2 and 4.3 containing the carbene crosslinking functionalizing agent 3.1, and then having a functionalized SBR) were prepared.

[0775] The amounts of various components, expressed as phr, and the steps of their addition are reported in Table 3 below.

[0776] Table 3: Compositions of elastomer compounds (carbene crosslinking functionalizing agent 3.1)

[0777] stage Phr ingredients Ex.4.1 Ex.4.2 Ex.4.3 contrast invention invention 1.0 SBR 100(137.5) 100(137.5) 100(137.5) 1.1 Reagent 3.1 -- 0.62 1.24 2.1 silicon dioxide 60 60 60 2.1 TESPD 4.8 4.8 4.8 2.2 stearic acid 2 2 2 2.2 ZnO 2 2 2 2.2 6PPD 2 2 2 3.1 S 1 1 1 3.1 CBS 3 3 3

[0778] in:

[0779] Phase 1.0-2.2: Non-productive steps or steps (i);

[0780] Phase 3.1: Productive steps or steps (ii);

[0781] SBR: SLR4630 styrene-butadiene copolymer with 25% styrene and 62% vinyl (based on butadiene content), with a 37.5 phr increment from Synthos' TDAE oil; Silica: ZEOSIL 1165 MP, supplier Solvay Rhodia Operations; TESPD: silanizing agent, bis-(triethoxysilylpropyl)disulfide, Si266, supplier: Evonik; Stearic acid: Stearin N, supplier Sogis; ZnO: from Zincol Ossidi; 6PPD: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine; Antioxidant, SantoflexTM 6PPD, supplier: Eastman; Sulfur: vulcanizing agent, supplier: Zolfindustria; CBS: N-cyclohexyl-2-benzothiazolylsulfonamide; Accelerator, Supplier: Lanxess.

[0782] The mixing was performed in multiple stages using a laboratory tangential rotor mixer (60 mL mixing chamber) from Brabender.

[0783] In the first stage (1-0), the elastomer was introduced and chewed for 30 seconds at 120°C (set temperature). In the subsequent stage (1.1), the crosslinking functionalizing agent 3.1 was introduced into mixtures 4.2 and 4.3 and mixed at 120°C for about 5 minutes, after which the functionalized polymer was unloaded, or, in the case of control compound 4.1, it remained unchanged. In the subsequent non-productive step, silica and TESPD (2.1) were added to the corresponding compound loaded in the same mixer, followed by stearic acid, ZnO, and 6PPD (2.2), and mixing was continued at 140°C for about 6 minutes, after which the compound was unloaded.

[0784] Finally, in the productive step (stage 3.1) using the same mixer, the vulcanizing agent (sulfur) and accelerator (CBS) are introduced, and mixing continues at 80°C for about 3 minutes, at which point the final rubber compound is unloaded.

[0785] The static and dynamic mechanical properties of the final rubber compound, the comparative rubber compound, and the rubber compound according to the present invention after vulcanization were analyzed using the above method.

[0786] The results of these analyses are reported in Table 4 below:

[0787] Table 4

[0788] Ex.4.1 Ex.4.2 Ex.4.3 contrast invention invention Reagent 3.1 -- 0.62phr 1.24phr CA0.1 (23℃) MPa 0.78 0.83 0.98 CA0.5 (23℃) MPa 1.64 1.56 2.07 Ca1 (23℃) MPa 2.64 2.48 3.52 Ca3 (23℃) MPa 11.84 11.54 14.01 CR (23℃) MPa 18.33 20.12 13.86 AR (23℃) ％ 400.68 435.21 305.10 E'(0℃ 100Hz) MPa 18.58 19.39 22.54 Tanδ (0℃ 100Hz) -- 0.777 0.747 0.675 E'(70℃ 100Hz) MPa 7.07 7.62 9.30 Tanδ (70℃ 100Hz) -- 0.146 0.141 0.138

[0789] The adhesive compound according to the invention in Example 4.2 containing 0.62 phr crosslinking functionalizer 3.1 exhibits an increase in E' modulus and a decrease in hysteresis, similar to those achievable with commercially available functionalized polymers.

[0790] Surprisingly, the increase in crosslinking does not adversely affect the tensile properties of the material.

[0791] The compound of Example 4.3 containing 1.24 phr crosslinking functionalizer 3.1 showed that the functionalization effect was strongly dependent on the amount of functionalizer, and it had much higher static and dynamic modulus values ​​than the reference compound, thus significantly reducing hysteresis, but also reducing CR and AR values.

[0792] Example 5

[0793] Preparation of adhesives containing a mixture of carbene crosslinking functionalizing agents and poorly compatible elastomers.

[0794] To evaluate the potential compatibilizing effect of the reagent of formula (I) on different elastomers in the blend, compounds containing two types of SBRs that are almost dissimilar to each other were prepared, specifically a control compound (e.g., 5.1, which does not contain a crosslinking functionalizer and therefore does not undergo any compatibilization) and a compound according to the invention (e.g., 5.2, which contains a carbene crosslinking functionalizer 3.1 in an amount selected in previous experiments at 0.62 phr). The preparation process was similar to that of Example 4. In this case, the crosslinking functionalizer was added and pre-reacted with only one of the two SBRs at a secondary activation temperature TB (see SBRA in Table 5 below) to form a single-functionalized SBR.

[0795] The amounts of the various components, expressed as phr, and the steps they are added to the rubber compound are reported in Table 5 below:

[0796] Table 5: Compositions containing rubber compounds that are almost dissimilar to SBR (Carbene crosslinking functionalizer 3.1)

[0797] stage Phr ingredients Ex.5.1 Ex.5.2 contrast invention 1.0 SBR A 50(68.75) 50(68.75) 1.1 Reagent 3.1 -- 0.62 2.0 SBR B (Incremental Oil) 50(68.75) 50(68.75) 2.1 silicon dioxide 60 60 2.1 TESPD 4.8 4.8 2.2 stearic acid 2 2 2.2 ZnO 2 2 2.2 6PPD 2 2 3.1 S 1 1 3.1 CBS 3 3

[0798] in:

[0799] Phase 1.0-2.2: Non-productive steps or steps (i);

[0800] Phase 3.1: Productive steps or steps (ii);

[0801] SBR A: NT 120 partially hydrogenated styrene-butadiene copolymer, degree of hydrogenation 93.5%, elastomer polymer with 37 phr TDAE oil / 100 phr dry elastomer polymer (phr in parentheses includes oil) increment, styrene 35%, vinyl 27%, Tg -31℃, density 0.92 g / cm³ 3 Supplier: ENEOS; SBR B: SLR4630 with 25% styrene and 62% vinyl (based on butadiene content), with an increment of 27.3% TDAE oil, supplier: Synthos; and other components as defined in Table 3 above.

[0802] The static and dynamic mechanical properties of the final rubber compound, the comparative rubber compound, and the rubber compound according to the present invention were analyzed using the above method.

[0803] The results of these analyses are reported in Table 6 below.

[0804] Table 6

[0805] Ex.5.1 Ex.5.2 contrast invention Reagent 3.1 -- 0.62phr CA0.1 (23℃) MPa 1.02 0.93 CA0.5 (23℃) MPa 2.20 2.19 Ca1 (23℃) MPa 3.52 3.53 Ca3 (23℃) MPa 14.71 14.76 CR (23℃) MPa 20.81 22.02 AR (23℃) ％ 391.55 414.25 E'(0℃ 100Hz) MPa 24.69 24.53 Tanδ (0℃ 100Hz) -- 0.640 0.626 E'(70℃ 100Hz) MPa 9.35 9.40 Tanδ (70℃ 100Hz) -- 0.135 0.134

[0806] Unlike the compound in Example 4, which contains only one type of SBR, the data reported in Table 6 do not show changes in modulus / hysteresis ratio, but tensile properties are significantly improved, as shown by the CR and AR values ​​of the compound according to the invention.

[0807] This significant change in tensile properties may be due to improved interaction at the interface between the two poorly compatible elastomeric polymers in the compound, which can be attributed to the reagent of formula (I) of the present invention.

[0808] Example 6

[0809] Preparation of elastomer compounds containing nitrobenzene crosslinking functionalizing agent (I)

[0810] Comparative elastomer compounds (e.g., 6.1, which do not contain the formula (I) reagent and therefore have an unaltered SBR) and elastomer compounds according to the invention (e.g., 6.2, which contain the azinon reagent (I) 3.4 and then have a functionalized SBR) were prepared. The preparation process was completely similar to the preparation process described in Example 4.

[0811] The amounts of the various components, expressed as phr, and the steps they are added to the rubber compound are reported in Table 7 below:

[0812] Table 7: Compositions for use in elastomer compounds (nitrogen benzene crosslinking functionalizing agent 3.4)

[0813] stage Ingredients (phr) Ex.6.1 Ex.6.2 contrast invention 1.0 SBR B (Incremental Oil) 80(110) 80(110) 1.0 BR 20 20 1.0 Reagent 3.4 -- 1.2 2.1 silicon dioxide 60 60 2.1 TESPD 4.8 4.8 2.2 stearic acid 2 2 2.2 ZnO 2 2 2.2 6PPD 2 2 3.1 S 1 1 3.1 CBS 3 3

[0814] in:

[0815] BR: BUNA CB25 high cis polybutadiene polymer, which is prepared in solution with a neodymium catalyst (supplier Lanxess), and other components as defined in Table 3 above.

[0816] Figure 8 The report includes reagents 3.4 and Overlapped IR spectra of the blend of 130 before (dashed line) and after (solid line) heat treatment at 140 °C show the reaction of the nitrogen bene with the polymer double bond at 2100 cm⁻¹. -1 The azide band disappeared at that location.

[0817] The static and dynamic mechanical properties of the final rubber compound, the comparative rubber compound, and the rubber compound according to the present invention were analyzed using the above method.

[0818] The results of these analyses are reported in Table 8 below:

[0819] Table 8

[0820]

[0821]

[0822] The data reported in Table 8 show that the increase in static modulus has a similar effect to that observed in Example 4.3, which is surprisingly independent of the decrease in tensile strength, which remains constant, while elongation decreases due to the increase in stiffness. Finally, the increase in dynamic shear modulus does not significantly increase hysteresis and the Payne effect.

[0823] In summary, the tests conducted and the results outlined above demonstrate that the reagent of formula (I) of the present invention, when incorporated into tire compounds, exhibits a significant curing effect without compromising tensile strength. Furthermore, it improves the compatibility of dissimilar polymers in the compound. The final compounds of the present invention exhibit optimal performance due to their combination of significant mechanical reinforcement, good tensile properties, and low hysteresis. These results support the use of the crosslinking functionalizing reagent (I) of the present invention in tire compounds as a substitute for or optionally in combination with conventional functionalized polymers. However, the reagent of the present invention possesses undeniable advantages, namely, its relatively simple and versatile preparation method and broad applicability even to low-reactive polymers.

Claims

1. A reagent of formula (I): (I) in: n is an integer from 1 to 3; B is an organic group capable of producing carbene or nitrobenes. A represents at least a divalent organic linker residue between the B group and the one or more tetrazolium groups, wherein A is covalently linked to the 2 or 5 position of the one or more tetrazolium groups, wherein the one or more tetrazolium groups are 2,5-disubstituted tetrazolium groups; R is an organic group covalently attached to the 5- or 2-position of the one or more tetrazoles, respectively, selected from the group consisting of linear or branched C1-C 10 alkyl; C6-C 20 aryl; C3-C 10 cycloalkyl; 5- or 6-membered saturated, unsaturated or aromatic monocyclic or bicyclic heterocyclyl containing at least one heteroatom selected from N, S, O, R in turn optionally substituted by at least one electron withdrawing group EW or at least one electron donating group ED, The reagent of formula (I) is characterized by the activation temperature (TB) of group B and one or more activation temperatures (T-Tetr) of the one or more tetrazolium, wherein the one or more activation temperatures (T-Tetr) are higher than the activation temperature (TB).

2. The reagent of formula (I) according to claim 1, wherein n=1 and the organic residue A is a divalent organic residue.

3. The reagent of formula (I) according to claim 1 or 2, wherein the organic residue A (linker) comprises at least one of the following or is composed of the following: C1-C 20 Saturated or unsaturated, straight-chain or branched alkylene groups, optionally containing one or more heteroatoms and / or one or more linking functional groups in the chain; C6-C 20 A arylene group; a monocyclic or bicyclic heterocyclic group having a saturated, unsaturated, or aromatic 5- or 6-membered ring containing at least one heteroatom selected from N, S, and O, wherein the alkylene group, arylene group, and heterocyclic group are optionally substituted, or combinations thereof.

4. The reagent of formula (I) according to claim 1 or 2, wherein at least one of the arylene and / or heterocyclic groups in said organic residue A is directly or by inserting a CH2- group to the tetrazolium.

5. The reagent of formula (I) according to claim 1 or 2, wherein the molecular weight of the organic residue A is less than 1000 g / mol.

6. The reagent of formula (I) according to claim 5, wherein the molecular weight of organic residue A is less than 300 g / mol.

7. The reagent of formula (I) according to claim 1 or 2, wherein the R group is selected from optionally substituted C6-C groups. 10 Aryl or heterocyclic group.

8. The reagent of formula (I) according to claim 7, wherein the R group is selected from phenyl, 3-chlorophenyl, 3,5-dichlorophenyl and thiophene.

9. The reagent of formula (I) according to claim 1 or 2, wherein the group B capable of generating carbene or azibene is selected from bisacrididine, diazo, enone, sulfonyl azide, azide and isocyanate.

10. The reagent of formula (I) according to claim 1, wherein n=1 and has formula (Ia) or (Ib): (Ia)(Ib) Wherein B, A, and R have the meaning according to claim 1.

11. The reagent of formula (I) according to claim 1, wherein n=1 and A is a divalent organic residue (linker) of formula A''-A', wherein A''- directly binds to group B-selected from C6-C 10 arylene groups, and optionally benzyl-fused monocyclic or bicyclic heterocyclic groups of aromatic compounds having a 5- or 6-membered ring containing at least one heteroatom selected from N, S, and O. A' may not exist, or if it does exist, it contains C6-C. 10 -Asyl, aromatic heterocyclic, C1-C 10 -alkylene-oxy-C6-C 10 -Alearyl- or C1-C 10 -alkylene-oxy-aromatic heterocyclic group, and it is bound to a tetrazolium through the aromatic moiety. B is a group capable of generating carbene or a sulfonyl azide group capable of generating nibond, and R may have the meaning according to claim 1.

12. The reagent of formula (I) according to claim 1, wherein n=1 and A is a divalent organic residue (linker) of formula A''-A', wherein A''- directly binds to group B-selected from C1-C 10 -alkylene-, C6-C 10 -arylene-, a phenyl-fused heterocyclic group containing at least one heteroatom selected from monocyclic or bicyclic N, S, and O, with a 5- or 6-membered ring, C1-C 10 -alkylene-C6-C 10 -Asaryl- and C1-C 10 alkylene-heterocyclic group, A' may not exist, or if it does exist, it contains C6-C. 10 -Asyl, aromatic heterocyclic, C1-C 10 -alkylene-oxy-C6-C 10 -Alearyl- or C1-C 10 -alkylene-oxy-aromatic heterocyclic group, and it is bound to a tetrazolium through the aromatic moiety. B is a azido group, a precursor of nitroben, and R can have the meaning according to claim 1.

13. The reagent of formula (I) according to claim 11 or 12, wherein A'' and A' are directly bound without any inserted linker functional groups.

14. The reagent of formula (I) according to claim 1 or 2, wherein the activation temperature TB of the carbene or azine group B precursor is less than 140°C, and / or the activation temperature T-Tetr of one or more of the tetrazolium components is not less than 140°C.

15. The reagent of formula (I) according to claim 14, wherein the activation temperature TB of the carbene or azine group B precursor is less than 130°C, and / or the activation temperature T-Tetr of one or more of the tetrazolium components is not less than 160°C.

16. A functionalized diene elastomer polymer obtained by reacting a diene elastomer polymer with at least one reagent of formula (I) according to any one of claims 1 to 15.

17. A method for preparing the functionalized diene elastomer polymer according to claim 16, the method comprising: -Provides diene elastomer polymers; - Provide a reagent of formula (I) according to any one of claims 1 to 15; - The diene elastomer polymer and the reagent of formula (I) are mixed and held at a temperature T1 above the activation temperature (TB) of the reagent of formula (I) and below one or more activation temperatures (T-Tetr) for a time sufficient to complete the functionalization reaction of the diene elastomer polymer to obtain a functionalized diene elastomer polymer.

18. The method of claim 17, wherein the temperature T1 is below 170°C.

19. The method of claim 18, wherein the temperature T1 is below 160°C.

20. The method according to claim 17 or 18, wherein the reagent of formula (I) is used in a weight percentage of 0.1% to 10% relative to the diene elastomer polymer.

21. An elastomer composition for use in tire rubber compounds, comprising at least: At least one diene elastomer polymer with a phr of -100 phr -At least one reinforcing filler with a minimum of 1 phr, - At least 0.1 phr of at least one reagent of formula (I) according to any one of claims 1 to 15; and -0 to 20 phr vulcanizing agent.

22. The elastomer composition according to claim 21, comprising at least one reagent of formula (I) in amounts of 0.1 phr to 10 phr.

23. An elastomeric tire compound obtained by mixing and optionally heating the elastomeric composition according to claim 21 or 22.

24. A method for preparing an elastomer tire compound according to claim 23, wherein the elastomer tire compound is vulcanized and optionally crosslinked, the method comprising: -(i) In one or more stages, mixing at least 100 phr of at least one diene elastomer polymer, at least 0.1 phr of at least one reagent of formula (I) according to any one of claims 1 to 15, and optionally other components other than a vulcanizing agent, maintaining the temperature always below one or more activation temperatures (T-Tetr) of the tetrazolium component in the reagent of formula (I), and at least for one mixing stage, above a value T1 above the activation temperature (TB) of group B in the same reagent of formula (I), to obtain a crosslinkable non-vulcanizable compound comprising the functionalized diene elastomer polymer (non-productive step). -(ii) The step of adding the vulcanizing agent and optionally other components of the vulcanizing package to the aforementioned rubber compound and mixing at a temperature T2 always lower than both the temperature (T-Tetr) for activating the tetrazolium component and the vulcanization temperature (TV) of the rubber compound to obtain a vulcanizable and crosslinkable rubber compound (production step); and -(iii) The step of vulcanizing and optionally crosslinking the aforementioned rubber compound by heating at a temperature T3 above the vulcanization temperature (TV) of the rubber compound and optionally also at one or more of the temperatures (T-Tetr) used to activate the tetrazolium component, to obtain a vulcanized and optionally crosslinked elastomer compound.

25. A vehicle wheel tire component comprising the elastomeric compound according to claim 23.

26. The vehicle wheel tire component according to claim 25, wherein the component is selected from the tread, underlayer, wear-resistant layer, sidewall, sidewall insert, miniature sidewall, liner, underliner, adhesive layer, bead filler, bead reinforcement layer and bead protection layer.

27. A vehicle wheel tire, comprising at least one tire component as claimed in claim 25 or 26.

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