Compounds, rubber mixtures containing the compounds, vehicle tires having at least one component comprising a rubber mixture, process for preparing the compounds, and use of the compounds as ageing stabilizers and / or antiozonants and / or colorants

Abstract

The present invention relates to a compound, to a rubber mixture containing said compound, to a vehicle tire comprising this rubber mixture in at least one component, to a process for the preparation of the compound and to the use of the compound as ageing stabilizer and / or antiozonant and / or colorant. The compound according to the invention is of formula (I) in which A is an aromatic group, optionally carrying further substituents, in which R 1 xi) aromatic groups, which optionally have a substituent selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups; and xii) linear, branched and cyclic aliphatic C1-C 12 xiii) aromatic and aliphatic C1-C 12 In one embodiment, the aryl group is selected from the group consisting of a aryl group and a aryl group. TIFF2024528687000016.tif30170

Description

[Technical field]

[0001] The present invention relates to a compound, a rubber mixture containing the compound, a vehicle tire comprising the rubber mixture in at least one component, a process for producing the compound, and the use of the compound as ageing stabilizer and / or antiozonant and / or dye. [Background technology]

[0002] Vehicle tires and technical rubber articles are known to employ polymeric materials, particularly rubber.

[0003] In case of long-term storage and especially in the intended use, which is often at high temperatures, natural rubber and synthetic polymers (such as IR, BR, SSBR, ESBR, etc.), as well as natural and synthetic oils, fats and lubricants, are subject to oxidation reactions that adversely affect their original desired properties. Depending on the type of polymer, the polymer chains shorten until the material liquefies or until subsequent hardening of the material occurs.

[0004] Ageing stabilizers therefore play a crucial role in the durability of vehicle tires and other technical rubber articles.

[0005] Known aging stabilizers are aromatic amines, e.g. 6-PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine), IPPD (N-isopropyl-N'-phenyl-p-phenylenediamine) or SPPD (N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine) It is.

[0006] These molecules are capable of reacting with oxygen or ozone or with free radicals that are formed, such as alkyl, alkoxy and alkylperoxy radicals, thereby scavenging them and thus protecting the rubber, etc., from further oxidation reactions.

[0007] However, a drawback of this substance class is that they are suspected of being carcinogenic.

[0008] Aging stabilizers that specifically react with ozone to achieve its scavenging are also called "antiozonants." Summary of the Invention [Problem to be solved by the invention]

[0009] The aim of the present invention is to provide new compounds which can be used in particular as ageing stabilizers for vehicle tyres or other industrial rubber articles, and which in particular have a lower potential hazard, in combination with a sufficient solubility in the respective matrix, for example in particular in polymers, which are intended to prevent the tendency to blooming whilst maintaining an optimal protection against oxygen and ozone, reducing the hazards to health. [Means for solving the problem]

[0010] This object is achieved by the compound according to the invention as claimed in claim 1, by the rubber mixture according to the invention which contains the compound and by the vehicle tyre according to the invention which comprises in at least one component thereof the rubber mixture according to the invention.

[0011] This object is further achieved by using the compounds as ageing stabilizers and / or antiozonants.

[0012] The compounds according to claim 1 may further be used as dyes.

[0013] This object is further achieved by the process according to the invention for the preparation of the compounds according to the invention.

[0014] The compound as claimed in claim 1 has the general formula I: [ka] [wherein A is an aromatic group optionally bearing additional substituents, and where R 1 teeth, xi) aromatic groups, wherein the aromatic groups optionally bear substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups; and xii) linear, branched and cyclic aliphatic C1-C 12 xiii) aromatic and aliphatic C1-C 12 Combination with groups is selected from the group consisting of In the formula, R 3 is a linear, branched and cyclic, saturated and unsaturated, aliphatic C1-C optionally bearing one or more halogen substituents; 12 groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups (wherein fluorine, bromine and chlorine are preferred), cyano groups, ester groups, ketone groups, ether groups and thioether groups, where n has a value of 0 or 1 or 2 or 3 or 4, where when n is 2 or 3 or 4, the group R 3 are, independently of each other, identical or different] has.

[0015] A is an aromatic group optionally bearing additional substituents; In the formula, R 1 benzyl and linear, branched and cyclic aliphatic C1-C 12 is selected from the group consisting of In the formula, R 3 Linear, branched and cyclic aliphatic C1-C 12 and aryl, cyano, halogen (wherein fluorine, bromine and chlorine are preferred), ether and thioether groups, where n has a value of 0 or 1 or 2 or 3 or 4, and where when n is 2 or 3 or 4, the group R 3 are, independently of each other, identical or different This is preferable.

[0016] It will be apparent to one skilled in the art that when n is 0 or 1 or 2 or 3, all remaining free positions in the benzene ring of the indole structure are hydrogen atoms.

[0017] Similarly, those skilled in the art will recognize the (R 3 ) n The bond representation of each of these groups naturally occurs at two or more (R 3 ) may simultaneously be located in the same positions already excluded by the tetravalency of the carbon atoms of the benzene ring.

[0018] In the context of the present invention, the class "C1-C 12 The description of "radical" should be understood to mean a radical having 1 to 12 carbon atoms. Independently, "C1" is also used to describe the position of the most highly oxidized carbon atom / highest priority carbon atom according to the Cahn-Ingold-Prelog rules (CIP). What is meant in the respective context will be clear to the skilled person.

[0019] The compounds according to the invention are indole derivatives and show a low potential hazard compared to known aging stabilizers based on aniline (possible cleavage products of 6-PPD). Comparison of the safety data sheets of the basic structure aniline and indole reveals that, unlike aniline, indole is neither genotoxic nor mutagenic. This is a crucial advantage, especially in technical applications such as vehicle tires or other rubber products, where rubber components may be liberated by wear or other degradation processes. Furthermore, the oxidation products of 6-PPD pose a particular hazard to coho salmon. It should therefore be assumed that this applies to aquatic organisms in general (Tian et al, Science, 2020 Z. Tian, ​​Science, 2021, 371(6525), 185-189).

[0020] In contrast, indole derivatives have been proposed in pharmaceutical compositions or compositions for skin care, as disclosed in US20200339581A1 and JP2004196699A.

[0021] Japanese Patent No. 06147585B2 discloses an indole derivative of formula S1) [ka] In Japanese Patent Publication No. 06147585B2, R 1 and R 2 is defined differently in this case.

[0022] Compared to indole derivatives from the prior art, such as those shown in formula S1), the compounds according to the invention have the advantage that they do not contain vulcanizable groups (such as -SH) that allow binding to rubber / polymers. The binding causes the molecule to be locally bound and therefore may not be effective in remote areas where oxidative stress occurs. The binding would therefore prevent the molecule from expressing its full protection as an ageing stabilizer and / or antiozonant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present invention includes all advantageous embodiments, among others, as reflected in the claims. The present invention also includes embodiments resulting from combinations of different features having different priorities relative to these features, in particular such that the invention also includes combinations of a first feature described as "preferred" or in the context of an advantageous embodiment with a further feature, for example described as "particularly preferred".

[0024] A is preferably selected from the group consisting of phenylene, naphthylene and anthracenylene groups, and phenylene, naphthylene and anthracenylene groups having one or more attached substituents, where the substituents are preferably linear, branched and cyclic aliphatic C1-C 12groups, and aryl groups, cyano groups, halogen groups (wherein fluorine, bromine and chlorine are preferred), ether groups and thioether groups.

[0025] It is particularly preferred if A is a phenylene group, thus a phenyl group carrying two or more substituents, which results in a particularly advantageous solubility of these compounds according to the invention in rubber mixtures, in particular for vehicle tyres and other industrial rubbers.

[0026] Indole groups and the group NHR on the benzene ring (of the phenylene group) 1 are preferably arranged in para to each other.

[0027] The compounds according to the invention have the formula II: [ka] [In the formula, R 1 teeth, xi) aromatic groups, wherein the aromatic groups optionally bear substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups; and xii) linear, branched and cyclic aliphatic C1-C 12 basis, and xiii) aromatic and aliphatic C1-C 12 Combination with groups wherein R 2 is a linear, branched and cyclic, saturated and unsaturated, aliphatic C1-C optionally bearing one or more halogen substituents; 12 groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups (wherein fluorine, bromine and chlorine are preferred), cyano groups, ester groups, ketone groups, ether groups and thioether groups; where m has a value of 0 or 1 or 2 or 3 or 4, and where m is 2 or 3 or 4, the group R 2 are, independently of one another, identical or different, In the formula, R 3is a linear, branched and cyclic, saturated and unsaturated, aliphatic C1-C optionally bearing one or more halogen substituents; 12 groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups (wherein fluorine, bromine and chlorine are preferred), cyano groups, ester groups, ketone groups, ether groups and thioether groups, where n has a value of 0 or 1 or 2 or 3 or 4, where when n is 2 or 3 or 4, the group R 3 are, independently of each other, identical or different] It is preferable that the compound has the structure:

[0028] Again, so that when n is 0 or 1 or 2 or 4, the free position on the benzene ring is a hydrogen atom.

[0029] (R 2 ) m and R 1 It will be equally clear to those skilled in the art that the representation of the HN bond should be understood as meaning that these groups can each be located at any position on the benzene ring, except, of course, not both at the same position at the same time, as would already be precluded by the tetravalency of the carbon atoms of the benzene ring.

[0030] It is preferred that n is 0 as applied to formulae I) and II).

[0031] base R 1 teeth, xi) aromatic groups, where the aromatic groups optionally have a substituent selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups; and xii) linear, branched and cyclic aliphatic C1-C 12 xiii) aromatic and aliphatic C1-C 12 Combination with groups is selected from the group consisting of:

[0032] An aromatic radical from subgroup xi) is, for example, preferably a phenyl radical.

[0033] The aromatic radicals of subgroup xi) may bear substituents.

[0034] As mentioned above, these are selected from the group consisting of halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether radicals.

[0035] It is preferred if the substituents are selected from the group consisting of ester radicals, ketone radicals, ether radicals and thioether radicals.

[0036] In a preferred embodiment, the aromatic radical is unsubstituted at the two carbon atoms adjacent to the C1 atom, i.e., the carbon atom bonded to the N atom. Thus, in the case of a benzene ring as a basic structure, it is preferred that there is no substituent at the ortho position relative to the N atom.

[0037] In a further preferred embodiment the aromatic radicals of subgroup xi) are unsubstituted.

[0038] R 1 is preferably linked to the nitrogen atom (N) via a tertiary carbon atom. Thus, the C1 atom is preferably a tertiary carbon atom.

[0039] In the context of the present invention, the term "tertiary carbon atom" should be understood to mean a carbon atom which is bonded to only one hydrogen atom.

[0040] This, compared to secondary and quaternary carbon atoms, results in a particularly good protective effect due to the presence of the compound in rubber mixtures, especially vehicle tires and other industrial rubber articles, thereby resulting in optimal reactivity, especially in relation to mechanisms related to ageing stabilization, and avoiding undesirable side reactions.

[0041] The mixed aromatic and aliphatic radicals of subgroup xiii) are, for example, preferably selected from the group consisting of benzyl and 1-phenylalkyl radicals having a total of 7 to 18 carbon atoms, in particular selected from the benzyl and 1-phenylethyl radicals, the 1-phenylalkyl radicals, in particular the 1-phenylethyl, being particularly preferred for the tertiary carbon atom.

[0042] R 1 is particularly preferably a branched alkyl group having 3 to 12 carbon atoms, in turn preferably having 3 to 8 carbon atoms. It is preferred if at least one branch is present on the C1 carbon, i.e. on the carbon atom bonded to the nitrogen atom (N), thus making the C1 atom a tertiary carbon atom.

[0043] R 1 is very particularly preferably selected from the 1,3-dimethylbutyl and cyclohexyl radicals, 1 is very particularly preferably a 1,3-dimethylbutyl group.

[0044] Radical R 2 are each independently the same or different, and are linear, branched, and cyclic, saturated and unsaturated aliphatic C1-C 12 radicals, aryl radicals which may carry one or more halogen substituents, halogen radicals, preferably fluorine, bromine and chlorine, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether radicals.

[0045] Enumerated radicals R 2 may already be attached to the respective benzene ring / precursor thereof, in particular by choosing the appropriate starting material.

[0046] It is preferred that m in formula II) is 0 (zero).

[0047] Indole groups and the group NHR on benzene (phenylene group) 1 are preferably arranged in para to each other.

[0048] In a preferred embodiment, the compound has formula III: [ka] It has the structure:

[0049] The compounds of formula III) make it possible to achieve optimal protection against oxidation and thus against aging, especially in polymers, and at the same time are significantly less harmful to health than, for example, 6-PPD or other representatives of this substance class, as mentioned above.

[0050] The inventive compounds of formula I), formula II), formula III) and all the above mentioned are particularly suitable as ageing stabilizers and / or antiozonants in vehicle tyres and / or technical rubber articles, in particular in air springs, bellows, conveyor belts, belts, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical applications or robotics, or shoe soles or parts thereof, and / or oils and / or lubricants.

[0051] The present invention therefore further provides the use of the compounds according to the invention as ageing stabilizers and / or antiozonants in vehicle tyres and / or industrial rubber articles, in particular in air springs, bellows, conveyor belts, belts, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical or robotic applications, or shoe soles or parts thereof, and / or oils and / or lubricants.

[0052] To use the compounds of Formula I), Formula II), Formula III), and all of the foregoing in the recited articles or materials, the compounds are used in compositions or are incorporated into the compositions.

[0053] In vehicle tires or other industrial rubber articles, said composition is especially present in a rubber mix.

[0054] The present invention further provides the use of the compounds of the formula I), II), III) and all of the above according to the invention as dyes in fibres and / or polymers and / or paper and / or (decorative) paints and coatings.

[0055] A further aspect of the present invention is a method comprising the steps of: a) Formula A) [ka] providing a compound of formula (I); b) reacting a compound of formula A) with hydrogen or a hydrogenation agent, in particular a hydride, and a ketone or aldehyde (R 1 =O), preferably with a ketone, in particular and preferably with methyl isobutyl ketone, to give the compound of formula I) [ka] Obtaining a compound of A method for preparing a compound of formula I comprising:

[0056] All of the foregoing are defined as groups R 1 and R 3 and n and A. Again, it is preferred if n is zero.

[0057] "Hydrogenation reagent" should be understood to mean a compound that brings about hydrogenation. Such reagents include hydrides, in particular metal hydrides, as known to those skilled in the art.

[0058] Suitable hydrides include, for example, sodium borohydride.

[0059] In the context of the present invention, hydrogen is explicitly mentioned as an alternative and is therefore not additionally listed under "hydrogenation reagents". Nevertheless, it will be understood that the term "hydrogenation reagents" encompasses all reagents that form hydrogen to perform in situ hydrogenation.

[0060] It is preferred if the reaction in step b) with hydrogen (H2) and a ketone or aldehyde, preferably a ketone, is carried out using a hydrogenation catalyst, preferably at a temperature of 50° C. to 70° C., in particular for example at 60° C. The reaction mixture is preferably subjected to hydrogen at a pressure of 15 to 25 bar, in particular for example at 20 bar, and subsequently preferably stirred for 1 to 20 hours, preferably for 8 to 13 hours, in particular for example for 10 hours.

[0061] In step b), the ketone is reacted with the following radical R 1 in the case of an aldehyde, it is therefore an aldehyde derivative.

[0062] For simplicity, the radical R 1 is the moiety that remains on the nitrogen atom after reaction with an aldehyde or ketone, so it is represented by the simplified formula R 1 =O is used for aldehydes or ketones.

[0063] It is preferred to use the ketone methyl isobutyl ketone.

[0064] Preference is given to process steps in which the reaction with hydrogen is carried out employing a suitable catalyst, which in the context of the present invention is referred to as a "hydrogenation catalyst".

[0065] It is preferred when the hydrogenation catalyst of the process is a noble metal catalyst, such as, in particular, palladium (Pd) or platinum (Pt). It is preferred when the noble metal is used on carbon (C), such as palladium on carbon (Pd / C).

[0066] Additionally, other known catalysts such as Raney nickel or copper chromite may also be used.

[0067] It is preferred if the reaction with hydrogen in step b) is carried out in a vessel suitable for relatively high pressures, such as in particular an autoclave or another pressure reactor.

[0068] In the above process, A is preferably a phenylene group and m is zero. The bonds on the benzene ring (of the phenylene group) are preferably para to each other.

[0069] As mentioned above, the present invention further provides a rubber mixture.

[0070] The rubber mixtures according to the invention contain compounds of formula I), in particular of formula II), in particular of formula III). They can in principle be any rubber mixture in which the novel inventive compounds, in particular of formula I), in particular of formula II), in particular of formula III), act as ageing stabilizers and / or antiozonants with low toxicity.

[0071] The rubber mixtures of the present invention contain at least one rubber.

[0072] It is preferred if the rubber mixture according to the invention contains 0.1 to 10 phr, particularly preferably 0.1 to 7 phr and very particularly preferably 1 to 6 phr of compounds of the formula I), in particular of the formula II) and in particular of the formula III).

[0073] The unit "phr" (parts per 100 parts by weight of rubber) used in this document is the conventional designation of quantities for mixture formulations in the rubber industry. The dosage of parts by weight of individual substances is used in this document to include all high molecular weight (M w based on 100 parts by weight of the total mass of rubber (whose molecular weight exceeds 20,000 g / mol).

[0074] In an advantageous embodiment of the invention, the rubber mixture according to the invention contains at least one diene rubber.

[0075] Thus, the rubber mixture may contain a diene rubber or a mixture of two or more different diene rubbers.

[0076] Diene rubbers are rubbers formed by polymerizing or copolymerizing dienes and / or cycloalkenes and therefore containing C=C double bonds in either the backbone or in side groups.

[0077] The diene rubber is preferably natural polyisoprene (NR), synthetic polyisoprene (IR), epoxidized polyisoprene (ENR), butadiene rubber (BR), butadiene-isoprene rubber, solution polymerized styrene-butadiene rubber (SSBR), emulsion polymerized styrene-butadiene rubber (ESBR), styrene-isoprene rubber, molecular weight M w is selected from the group consisting of liquid rubber having a molecular weight greater than 20,000 g / mol, halobutyl rubber, polynorbornene, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber, nitrile rubber, chloroprene rubber, acrylate rubber, fluororubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-butadiene terpolymer, hydrogenated acrylonitrile butadiene rubber, and hydrogenated styrene-butadiene rubber.

[0078] Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber and / or ethylene-propylene-diene rubber are used in particular in the manufacture of industrial rubber articles, such as belts, drive belts and hoses and / or shoe soles, etc. Mixture compositions known to those skilled in the art for these rubbers, specific in terms of fillers, plasticizers, vulcanization systems and additives, are preferably employed.

[0079] The natural and / or synthetic polyisoprene of all embodiments can be cis-1,4-polyisoprene or 3,4-polyisoprene. However, it is preferred to use cis-1,4-polyisoprene with a cis-1,4 ratio of more than 90% by weight. Firstly, such polyisoprene is accessible by stereospecific polymerization in solution with Ziegler-Natta catalyst or with fine lithium alkyl. Secondly, natural rubber (NR) is such cis-1,4-polyisoprene that the cis-1,4 content in natural rubber is more than 99% by weight.

[0080] Mixtures of one or more natural polyisoprenes with one or more synthetic polyisoprenes are further contemplated.

[0081] In the context of the present invention, the term "natural rubber" should be understood to mean natural rubber obtainable from the Hevea rubber tree and from "non-Hevea" sources, such as the guayule shrub and dandelions, such as TKS (Taraxacum kok-saghyz).

[0082] If the rubber mixture of the present invention contains butadiene rubber (i.e. BR, polybutadiene), this may be of any type known to those skilled in the art. These include those called high-cis and low-cis types, where polybutadienes with a cis content of 90% or more by weight are called high-cis types and polybutadienes with a cis content of less than 90% by weight are called low-cis types. An example of a low-cis polybutadiene is Li-BR (lithium catalyzed butadiene rubber) with a cis content of 20% to 50% by weight. With high-cis BR, particularly good properties and low hysteresis are achieved in the rubber mixture.

[0083] The polybutadienes employed may be end-group-modified and / or functionalized along the polymer chain with modifications and functionalizations. The modifications may be selected from modifications with hydroxyl groups and / or ethoxy groups and / or epoxy groups and / or siloxane groups and / or amino groups and / or aminosiloxane and / or carboxyl groups and / or phthalocyanine groups and / or silane-sulfide groups. However, further modifications known to those skilled in the art, also called functionalizations, are also useful. Metal atoms may be constituents of such functionalizations.

[0084] If at least one styrene-butadiene rubber (styrene-butadiene copolymer) is present in the rubber mixture, it may be selected from solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized styrene-butadiene rubber (ESBR), it being possible to employ a mixture of at least one SSBR and at least one ESBR. The terms "styrene-butadiene rubber" and "styrene-butadiene copolymer" are used synonymously in the context of the present invention.

[0085] The styrene-butadiene copolymers employed may be end-group-modified and / or functionalized along the polymer chain by the modifications and functionalizations mentioned above for polybutadiene.

[0086] The at least one diene rubber is preferably selected from the group consisting of natural polyisoprene (NR, natural rubber), synthetic polyisoprene (IR), butadiene rubber (BR), solution polymerized styrene-butadiene rubber (SSBR), emulsion polymerized styrene-butadiene rubber (ESBR), butyl rubber (IIR) and halobutyl rubber.

[0087] In a particularly preferred embodiment of the present invention, the at least one diene rubber is selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), butadiene rubber (BR), solution polymerized styrene-butadiene rubber (SSBR) and emulsion polymerized styrene-butadiene rubber (ESBR).

[0088] In a particularly advantageous embodiment of the invention, the rubber mixture comprises at least one natural polyisoprene (NR) and / or synthetic polyisoprene (IR) preferably in an amount of 50 to 100 phr, in one particularly advantageous embodiment of the invention in an amount of 80 to 100 phr, very particularly preferably 95 to 100 phr, then preferably 100 phr. Such rubber mixtures exhibit in particular optimized tear and wear properties combined with good processability and reversion stability.

[0089] If the rubber mixture contains less than 100 phr of NR and / or IR, the rubber mixture preferably contains, as further rubber, at least one diene rubber selected from the group consisting of butadiene rubber (BR), solution polymerized styrene-butadiene rubber (SSBR) and emulsion polymerized styrene-butadiene rubber (ESBR).

[0090] In a further particularly advantageous embodiment of the invention, the rubber mixture comprises at least one natural polyisoprene (NR), preferably in an amount of 5 to 55 phr, and in one particularly advantageous embodiment of the invention in an amount of 5 to 25 phr, very particularly preferably in an amount of 5 to 20 phr. Such rubber mixtures exhibit particularly good processability and reversion stability as well as optimized tear properties and optimal rolling resistance characteristics.

[0091] In a further particularly advantageous embodiment of the invention, the rubber mixture comprises at least one polybutadiene (BR, butadiene rubber), preferably in an amount of 10 to 80 phr, particularly preferably 10 to 50 phr and in a particularly advantageous embodiment of the invention in an amount of 15 to 40 phr, whereby particularly good tear and wear properties as well as optimal braking characteristics of the rubber mixture according to the invention are achieved.

[0092] In a further particularly advantageous embodiment of the invention, the rubber mixture comprises at least one solution polymerized styrene-butadiene rubber (SSBR), preferably in an amount of 10 to 80 phr, particularly preferably 30 to 80 phr, and in one particularly advantageous embodiment of the invention in an amount of 50 to 70 phr. This achieves particularly good rolling resistance properties of the rubber mixture according to the invention. In a particularly advantageous embodiment of the invention, the SSBR is employed in combination with at least one further rubber in order to achieve an optimal and balanced property profile.

[0093] It is preferred if the rubber mixture contains at least one filler, preferably in an amount of 30 to 500 phr, particularly preferably in an amount of 50 to 400 phr, then preferably in an amount of 80 to 300 phr.

[0094] In an advantageous embodiment of the invention, the filler is a reinforcing filler, preferably selected from the group consisting of carbon black and silicon dioxide.

[0095] Suitable carbon blacks include any carbon black type known to those skilled in the art. It is preferred if the carbon black is selected from technical carbon black and pyrolytic carbon black, with technical carbon black being more preferred.

[0096] The carbon black preferably has an iodine value according to ASTM D1510, also known as iodine adsorption, of 30 to 250 g / kg, preferably 30 to 180 g / kg, particularly preferably 40 to 180 g / kg, and further particularly preferably 40 to 130 g / kg, and a DBP value according to ASTM D2414 of 30 to 200 ml / 100 g, preferably 70 to 200 ml / 100 g, and particularly preferably 90 to 200 ml / 100 g.

[0097] The DBP value according to ASTM D2414 determines the specific absorption volume of dibutyl phthalate in carbon black or light colored fillers.

[0098] The use of such types of carbon black in rubber mixtures, particularly for vehicle tires, ensures an optimal compromise between wear resistance and heat storage, which in turn affects the ecologically relevant rolling resistance.

[0099] Particularly suitable and preferred carbon blacks are those having an iodine adsorption number of 80 to 110 g / kg and a DBP number of 100 to 130 ml / 100 g, such as in particular carbon black of type N 339.

[0100] The silicon dioxide is preferably amorphous silicon dioxide, for example precipitated silica, also called precipitated silicon dioxide. However, it is alternatively possible to use, for example, pyrogenic silicon dioxide.

[0101] However, 35 to 400 m 2 / g, preferably 35 to 350m 2 / g, more preferably 85 to 320 m 2 / g, most preferably 120 to 235 m 2 / g nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) and 30-400 m 2 / g, preferably 30 to 330m 2 / g, more preferably 80 to 300m 2 / g, most preferably 115 to 200m 2 It is particularly preferred to use finely divided precipitated silicas having a CTAB surface area (according to ASTM D 3765) of 10 ...

[0102] In a particularly advantageous embodiment of the invention, the rubber mixture contains at least one silica as filler, preferably in an amount of 30 to 500 phr, particularly preferably in an amount of 50 to 400 phr, then preferably in an amount of 80 to 300 phr.

[0103] In these amounts, silica is especially present as the sole or predominant filler (greater than 50% by weight, based on the total amount of filler).

[0104] In a further advantageous embodiment of the invention, the rubber mixture contains at least one silica as further filler, preferably in an amount of 5 to 100 phr, particularly preferably 5 to 80 phr, then preferably 10 to 60 phr.

[0105] In these amounts, the silica is particularly present as an additional filler, especially in addition to other primary fillers such as carbon black.

[0106] The terms "silicic acid" and "silica" are used synonymously in the context of the present invention.

[0107] In a particularly advantageous embodiment of the invention, the rubber mixture according to the invention contains from 0.1 to 60 phr, preferably from 3 to 40 phr, particularly preferably from 5 to 30 phr and very particularly preferably from 5 to 15 phr of at least one carbon black. In these amounts, the carbon black is in particular present as a further filler, in addition to the main filler, such as silica.

[0108] In a further advantageous embodiment of the invention, the rubber mixture according to the invention contains from 30 to 300 phr, preferably from 30 to 200 phr, particularly preferably from 40 to 100 phr, of at least one carbon black. In these amounts, the carbon black is present alone or as the main filler, and therefore optionally in combination with silica in the amounts towards the lower limits mentioned above.

[0109] In a particularly advantageous embodiment of the invention, the rubber mixture contains from 5 to 60 phr, particularly preferably from 5 to 40 phr, of at least one carbon black and from 50 to 300 phr, preferably from 80 to 200 phr, of at least one silica.

[0110] The rubber mixture may further contain further reinforcing or non-reinforcing fillers.

[0111] In the context of the present invention, further (non-reinforcing) fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide, or rubber gels and fibres (eg aramid fibres, glass fibres, carbon fibres, cellulose fibres).

[0112] Further optional reinforcing fillers include, for example, carbon nanotubes (CNTs), such as discrete CNTs, hollow carbon fibers (HCFs) and modified CNTs containing one or more functional groups, such as hydroxy, carboxy and carbonyl groups, graphite and graphene, and what are known as "carbon-silica dual phase fillers."

[0113] In the context of the present invention, zinc oxide is not included in the filler.

[0114] The rubber mixture may further contain conventional additives in conventional parts by weight, which are preferably added in at least one primary mixing stage during the preparation of said mixture. These additives include: a) ageing stabilizers known in the art, For example, p-phenylenediamines, such as N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine (SPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), or dihydroquinolines, such as 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), b) activators, such as zinc oxide and fatty acids (e.g. stearic acid) and / or other activators, such as zinc complexes, such as zinc ethylhexanoate; c) activators and / or agents for binding fillers, in particular carbon black or silica, such as S-(3-aminopropyl)thiosulfate and / or its metal salts (carbon black binding) and silane coupling agents (silica binding); d) antiozonant waxes; e) resins, especially tackifying resins; f) mastication aids, such as 2,2'-dibenzamidodiphenyl disulfide (DBD); g) processing aids, in particular fatty acid esters and metal soaps, for example zinc soaps and / or calcium soaps; h) plasticizers, for example in particular aromatic, naphthenic or paraffinic mineral oil plasticizers, for example MES (Mild Extraction Solvates), preferably having a content of polycyclic aromatic compounds of less than 3% by weight according to method IP 346, or RAE (Residual Aromatic Extract), or TDAE (Processed Distillate Aromatic Extract), or Rubber to Liquid (RTL) oils or Biomass to Liquid (BTL) oils, or triglycerides, for example rapeseed oil or factice, or hydrocarbon resins or liquid polymers with an average molecular weight (determined by GPC = Gel Permeation Chromatography in accordance with BS ISO 11344:2004) of 500 to 20 000 g / mol.

[0115] If a mineral oil is used, it is preferably selected from the group consisting of DAE (distillate aromatic extract), RAE (residual aromatic extract), TDAE (treated distillate aromatic extract), MES (light extract solvate), and naphthenic oils.

[0116] In a particularly advantageous embodiment, the rubber mixture according to the invention does not contain, in addition to the inventive compounds of formula I), in particular of formula II) and / or III), an ageing stabilizer from the group of p-phenylenediamines, in particular those listed above under a). In a particularly preferred embodiment, the rubber mixture according to the invention contains 0 to 0.1 phr, in particular 0 phr, of further ageing stabilizers based on p-phenylenediamines, preferably selected from the group consisting of, in particular, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine (SPPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD).

[0117] The very small amounts of p-phenylenediamine present according to the invention, preferably 0 to 0.1 phr, particularly preferably 0 phr, as well as the compounds of formula I), in particular formula II), in particular formula III), make it possible to achieve an equivalent protective effect with lower toxicity.The compounds of the invention of formula I), in particular formula II), in particular formula III), replace the listed p-phenylenediamines known in the prior art.

[0118] In a further advantageous embodiment of the present invention, since at least one further representative of the listed p-phenylenediamine aging stabilizers is present, the compounds according to the invention only partially replace the p-phenylenediamines known in the prior art, which also achieve the advantages according to the present invention, but only to a less than optimal extent.

[0119] In an advantageous embodiment, an ageing stabilizer of the dihydroquinoline type, such as TMQ, is present in the rubber mixture in addition to the compound of formula I) according to the invention. The amount of dihydroquinoline, in particular TMQ, present is preferably from 0.1 to 3, in particular from 0.5 to 1.5 phr.

[0120] The antiozonant waxes (group d above) are considered separately and, in a preferred embodiment of the invention, are present in the rubber mixture regardless of whether or not additional ageing stabilizers a) are present.

[0121] The silane coupling agent may be of any type known to those skilled in the art.

[0122] Additionally, one or more different silane coupling agents may be used in combination with one another, so that a rubber mixture may contain a mixture of different silanes.

[0123] Silane coupling agents react with surface silanol groups or other polar groups of silicon dioxide, especially silica, during mixing of the rubber / rubber mixture (in situ) or in pretreatment (pre-modification) situations, even before the addition of the filler to the rubber.

[0124] Coupling agents known from the prior art are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group as leaving group on the silicon atom and other functional groups which, possibly after cleavage, are capable of entering into a chemical reaction with the double bonds of the polymer. The latter groups may include, for example, the following chemical groups: -SCN, -SH, -NH2 or -S x -(where x=2~8).

[0125] The silane coupling agents which can be used are therefore, for example, 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane or 3,3'-bis(triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms, such as 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT), the corresponding disulfides (TESPD) or other mixtures of sulfides having 1 to 8 sulfur atoms with different sulfides. TESPT can also be added, for example, as a mixture with carbon black (trade name X50S®, manufactured by Evonik).

[0126] Blocked mercaptosilanes, such as known from WO 99 / 09036, can also be used as silane coupling agents. It is also possible to use silanes described in WO 2008 / 083241A1, WO 2008 / 083242A1, WO 2008 / 083243A1 and WO 2008 / 083244A1. Usable silanes include, for example, those sold by Momentive in the USA in numerous variants under the name NXT, such as in particular 3-octanoylthio-1-propyltriethoxysilane, or those sold by Evonik Industries under the name VP Si 363®.

[0127] The total proportion of further additives is preferably between 3 and 150 phr, more preferably between 3 and 100 phr, most preferably between 5 and 80 phr.

[0128] Zinc oxide (ZnO) may be included in the overall proportion of further additives in the amounts mentioned above.

[0129] This can be any type of zinc oxide known to the person skilled in the art, for example ZnO granules or powder. Conventionally used zinc oxides usually have a BET specific surface area of ​​less than 10 m2 / g. However, it is also possible to use zinc oxides with a BET surface area of ​​10 to 100 m2 / g, for example the so-called "nano zinc oxide".

[0130] The rubber mixtures of the present invention are preferably used in vulcanized form, especially for vehicle tires or other vulcanized industrial rubber articles.

[0131] The terms "vulcanization" and "crosslinking" are used synonymously in the context of the present invention.

[0132] The vulcanization of the rubber mixture of the present invention is preferably carried out in the presence of sulfur and / or sulfur donors with the aid of vulcanization accelerators, some of which can simultaneously act as sulfur donors, selected from the group consisting of thiazole vulcanization accelerators, mercapto vulcanization accelerators, sulfenamide vulcanization accelerators, thiocarbamate vulcanization accelerators, thiuram vulcanization accelerators, thiophosphate vulcanization accelerators, thiourea vulcanization accelerators, xanthogenate vulcanization accelerators and guanidine vulcanization accelerators.

[0133] It is preferred to use a sulfenamide accelerator selected from N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazyl-2-sulfenamide morpholide (MBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and guanidine accelerators such as diphenylguanidine (DPG).

[0134] The sulfur donor material used can be any sulfur donor material known to those of skill in the art.

[0135] Vulcanization retarders may also be present in the rubber mixture.

[0136] In other cases, the preparation of the rubber mixture according to the invention is preferably carried out by processes customary in the rubber industry, which include first preparing a primary mixture in one or more mixing stages, which contains all the components except the vulcanization system (e.g. sulfur and vulcanization-influencing substances), and the final mixture is produced by adding the vulcanization system in the final mixing stage.

[0137] The final mixture may be further processed and formed into a suitable shape, for example, by an extrusion operation or by calendering.

[0138] The rubber mixture according to the invention is particularly suitable for use in vehicle tires, especially pneumatic vehicle tires.In principle, its use in all tire components, especially outer components, particularly preferably in the flange profile, tread and / or sidewall, is conceivable.In the case of treads with a cap / base structure, the rubber mixture according to the invention is preferably used at least in the cap.

[0139] For use in vehicle tires, the mixture, as a finished pre-vulcanized mix, is preferably formed into the corresponding shape of the outer component and applied in known manner during the manufacture of green vehicle tires.

[0140] The production of the rubber mixture according to the invention for use as any other body mixture in vehicle tires is carried out as described above. The difference lies in the shaping after the extrusion operation / calendering of the mixture. The shape of the not yet vulcanized rubber mixture thus obtained for one or more different body mixtures is then subjected to the production of green tires.

[0141] Here, "body mix" refers essentially to the rubber mix for the inner components of the tire, such as the squeegee, inner liner (inner layer), core profile, belt, shoulder, belt profile, carcass, bead reinforcement, bead profile, flange profile and bandage.

[0142] The green tire, which is not yet cured, is then cured.

[0143] For the use of the rubber mixture of the invention in drive belts and other belts, in particular conveyor belts, the extruded, not yet vulcanized mixture is brought into a suitable shape and is often provided, simultaneously or subsequently, with reinforcing elements, such as synthetic fibers or steel cords, usually resulting in a multi-ply structure consisting of one and / or more plies of the rubber mixture, one and / or more plies of identical and / or different reinforcing elements and one and / or more further plies of the same and / or other rubber mixtures.

[0144] The present invention further provides a vehicle tyre comprising a rubber mixture according to the invention containing in at least one of its constituents a compound according to the invention.

[0145] The vulcanized vehicle tire in at least one component contains a vulcanizate of at least one rubber mixture according to the invention. It is known to those skilled in the art that most substances present, such as rubber, may be present already after mixing or only after vulcanization in a chemically modified form.

[0146] In the context of the present invention, "vehicle tires" should be understood to mean pneumatic vehicle tires and solid rubber tires, including industrial tires, as well as tires for construction vehicles, trucks, cars and motorcycles.

[0147] It is preferred if the vehicle tyre according to the invention comprises the rubber mixture according to the invention in at least one external component, which external component is preferably the tread, the sidewall and / or the flange profile.

[0148] Thus, the vehicle tyre according to the invention may comprise the rubber mixture according to the invention comprising the inventive compound of formula I), in particular of formula II), in particular of formula III), in several components, optionally in a compatible composition. EXAMPLES

[0149] The present invention will now be more specifically clarified with reference to the following examples.

[0150] As a preferred embodiment of the compounds of formula I) or II), the compounds of formula III) are represented by formula XI): [ka] As shown in Figure 1, it was prepared as follows.

[0151] 5.40 g (25.9 mmol, 1 eq) of 2-(4-aminophenyl)-1H-indole, 1.09 g of platinum on carbon (Pt / C) (5%) (0.2 g for 4.67 mmol of substrate) and 50.0 ml of methyl isobutyl ketone (MIBK) were weighed into a stainless steel autoclave equipped with a Teflon liner. The reaction mixture was then subjected to hydrogen at a pressure of 20 bar and stirred at 60° C. for 10 hours. At the end of the reaction, the excess hydrogen was released and the suspension was filtered through Celite® and washed with ethanol. The filtrate was evaporated to dryness and dried under vacuum. It was recrystallized from cyclohexane. A greyish-purple solid was obtained; yield 5.40 g (71% of theory). 1 H-NMR (Nuclear Magnetic Resonance) (500MHz,DMSO-d6)δ=11.16(s,1H),7.56(d,J=8.6Hz,2H),7.43(dd,J=7.7,1.1Hz,1H),7.32(dd, J=7.9,1.0Hz,1H),7.00(ddd,J=8.1,7.0,1.2Hz,1H),6.93(ddd,J=8.0,7.0,1.1Hz,1H),6.63(d,J=8.6Hz,2H), 6.57(d,J=1.4Hz,1H),5.56(d,J=8.5Hz,1H),3.56-3.47(m,1H),1.74(dt,J=13.5,6.7Hz,1H),1.47(dt,J=13.9 ,7.1Hz,1H),1.25(dt,J=13.5,6.9Hz,1H),1.11(d,J=6.2Hz,3H),0.93(d,J=6.6Hz,3H),0.89(d,J=6.6Hz,3H).

[0152] 13C-NMR(126MHz,DMSO-d6)δ=148.5,139.6,137.1,129.6,126.6,120.7,119.7 ,119.5,119.4,112.7,111.2,95.8,46.4,45.8,26.8,25.0,23.2,23.1,21.2.

[0153] ESI-MS (electrospray ionization mass spectrometry) [M+H] + =293.

[0154] Melting point: 142°C.

[0155] Measurement of oxidative induction time (OIT) Compounds of formula III) were investigated under laboratory conditions for their potential protective effect as aging stabilizers by measuring the oxidation induction time.

[0156] For this purpose, the compound of formula III and 6-PPD were in each case mixed with a polymer (liquid synthetic polyisoprene (IR), LIR-50, Kuraray, weight average molecular weight distribution M w = 54000g / mol, glass transition temperature T g =-63°C) and heated at a constant temperature (180°C) until the onset of oxidation (starting temperature 35°C, heating rate of 20 K / min (Kelvin / min) to 170°C, heating rate of 1 K / min to 180°C; purge gas: nitrogen (N2), volumetric flow rate 50 ml / min). The specimen was kept isothermal at 180°C for 5 min under N2 atmosphere, then the atmosphere was switched to O2 atmosphere (volume flow rate 50 ml / min).

[0157] DSC (differential scanning calorimetry) was used to determine the oxidation via peaks.

[0158] The time (min) until oxidation was measured.

[0159] The results compared with the known aging stabilizer 6-PPD are summarized in Table 1.

[0160] [Table 1]

[0161] Considering the measurement accuracy of ±(plus / minus) 10 minutes, it is clear that the compound of formula III) is a suitable alternative to the more health-hazardous compound 6-PPD.

[0162] For use in rubber mixtures for vehicle tyres, the compounds of the invention of formula I), e.g. of formula II), are added in one of the mixing stages during the preparation of the rubber mixture in a manner known to those skilled in the art, instead of ageing stabilizers known to those skilled in the art, such as, for example, 6PPD, 7PPD or IPPD.

[0163] Therefore, compounds of formula III) were incorporated into exemplary rubber mixtures according to the invention, as shown in Table 2. The resulting examples of the invention are labeled E1.

[0164] Serving as a comparison is rubber mixture V1 which contains 6PPD instead of the compound of formula III) as ageing stabilizer, the rest of the composition being identical. The amounts in Table 2 are expressed in phr.

[0165] The mixtures were prepared according to the process customary in the rubber industry in laboratory mixers with a volume of 300 ml to 3 liters under standard conditions in three stages: in the first mixing stage (premixing stage), all the components except the vulcanization system (sulfur and vulcanization-affecting agents) were mixed at 145°C to 165°C, with a target temperature of 152°C to 157°C, for 200 to 600 seconds. In the second stage, the mixture from the first stage was mixed again. In the third stage (final mixing stage), the vulcanization system was added to obtain the final mixture, the mixing was carried out at 90°C to 120°C for 180 to 300 seconds.

[0166] Test specimens were produced from all mixtures by vulcanization under pressure at 160°C–170°C after t95–t100 (measured using a moving die rheometer according to ASTM D 5289-12 / ISO 6502).

[0167] Also, some of the specimens of both V1 and E1 were aged (70°C in air for 28 days).

[0168] For all specimens the following material properties typical for the rubber industry were determined: Resilience at room temperature (RT) according to ISO 4662 or ASTM D 1054 Stress values ​​at 300% elongation (M 300) and breaking elongation at room temperature (RT) according to DIN 53 504

[0169] For V1 and E1, the difference between the values ​​of unaged and aged samples was determined.

[0170] The values ​​obtained for V1 were in each case normalized to 100% for reference.

[0171] The values ​​obtained for E1 (difference between unaged and aged) are reported as % performance against this respective V1 criterion, with values ​​above 100% being favored.

[0172] As is evident from Table 2, the compounds of the invention of formula III), as representative of the compounds of formula I), provide improved aging stabilization, since important properties such as stress value at 300% elongation (300 modulus), elongation at break and rebound resilience are in each case at higher levels for E1 than for V1 after aging.

[0173] [Table 2]

Claims

1. Formula I): 【Chemical 1】 wherein A is selected from the group consisting of phenylene, naphthylene, and anthracenylene groups, and phenylene, naphthylene, and anthracenylene groups bearing one or more substituents, wherein the substituents are selected from linear, branched, and cyclic aliphatic C １ ~C １２ groups, wherein R １ teeth, xi) aromatic group, and xii) branched and cycloaliphatic C １ ~C １２ basis, and xiii) an aromatic group and an aliphatic C １ ~C １２ Combination with groups wherein R ３ is linear, branched and cyclic, saturated and unsaturated, aliphatic C １ ~C １２ and aryl groups, wherein n has a value of 0 or 1 or 2 or 3 or 4, and when n is 2 or 3 or 4, the group R ３ are, independently of each other, identical or different.

1. A rubber mixture containing a compound of formula (I) above, wherein the rubber mixture contains at least one diene rubber.

2. The compound has formula II: 【Chemistry 2】 [In the formula, R １ teeth, xi) aromatic group, and xii) branched and cycloaliphatic C １ ~C １２ base, and xiii) an aromatic group and an aliphatic C １ ~C １２ Combination with groups wherein R ２ is linear, branched and cyclic, saturated and unsaturated, aliphatic C １ ~C １２ and aryl groups; In the formula, m takes the value 0 or 1 or 2 or 3 or 4, and when m is 2 or 3 or 4, the group R ２ are independently the same or different, and in the formula R ３ is linear, branched and cyclic, saturated and unsaturated, aliphatic C １ ~C １２ and aryl groups, wherein n has a value of 0 or 1 or 2 or 3 or 4, and when n is 2 or 3 or 4, the group R ３ are, independently of each other, identical or different.

2. The rubber mixture according to claim 1, characterized in that it has the structure:

3. 3. A rubber mixture according to claim 1, wherein n is 0.

4. R １ 3. Rubber mixture according to claim 1 or 2, characterized in that is linked to the nitrogen atom (N) via a tertiary carbon atom.

5. R １ 3. Rubber mixture according to claim 1, characterized in that is a branched alkyl radical having 3 to 12 carbon atoms.

6. R １ 3. A rubber mixture according to claim 1, wherein is selected from 1,3-dimethylbutyl radicals and cyclohexyl radicals.

7. 3. A rubber mixture according to claim 2, characterized in that m is 0 (zero).

8. The compound has formula III: 【Chemistry 3】 3. A rubber mixture according to claim 1 or 2, characterized in that it has the structure

9. 3. The rubber mixture according to claim 1 or 2, comprising at least one diene rubber selected from the group consisting of natural polyisoprene (NR rubber), synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene butadiene rubber (SSBR), emulsion-polymerized styrene butadiene rubber (ESBR), butyl rubber (IIR) and halobutyl rubber.

10. A vehicle tire comprising, at least in one of its components, a rubber mixture according to claim 1 or 2.

11. A vehicle tire comprising a rubber mixture according to claim 1 or 2 in at least one outer component, said outer component being the tread, the sidewall and / or the rim strip.

12. Use of a compound as defined in claim 1 or 2 as an ageing stabilizer in vehicle tires.

13. Formula I): 【Chemistry 4】 wherein A is a phenylene group, and １ is a branched alkyl radical having 3 to 12 carbon atoms, In the formula, R ３ is a linear, branched and cyclic, saturated and unsaturated, aliphatic C optionally bearing one or more halogen substituents; １ ~C １２ groups, aryl groups optionally bearing one or more halogen substituents, and halogen, cyano, ester, ketone, ether and thioether groups, wherein n takes the value 0. Compound.

14. Formula III): 【Chemistry 5】 14. The compound of claim 13, characterized in that it has the structure:

15. The following process steps: a) Formula A) 【Chemistry 6】 providing a compound of formula (I); b) reacting said compound of formula A) with hydrogen or a hydrogenation reagent and a ketone or aldehyde to produce a compound of formula I) 【Chemistry 7】 A step of obtaining a compound of A method for preparing a compound of formula I comprising: In the formula, A is a phenylene group, In the formula, R １ is a branched alkyl radical having 3 to 12 carbon atoms, In the formula, R ３ is a linear, branched and cyclic, saturated and unsaturated, aliphatic C optionally bearing one or more halogen substituents; １ ~C １２ groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups, wherein n takes the value 0; method.

16. Step b) in which hydrogen (H ２ 16. The process according to claim 15, characterized in that the reaction of hydroxybenzoates (H2O, H2O, HCl) with the ketone or aldehyde is carried out using a hydrogenation catalyst at a temperature between 50°C and 70°C, the reaction mixture being subjected to hydrogen at a pressure between 15 and 25 bar, and the reaction being carried out in an autoclave or another pressure reactor.

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