Compounds, rubber mixtures containing the compounds, vehicle tires having components comprising the rubber mixtures, processes for producing the compounds, and uses of the compounds

Abstract

This invention relates to compounds, rubber blends containing the compounds, vehicle tires comprising the rubber blends in at least one component, methods for producing the compounds, and the use of the compounds as aging stabilizers and / or anti-ozone agents and / or dyes. The compounds according to the invention have formula (I), wherein A is an aromatic group optionally with additional substituents, and wherein R... 1 The following are selected from the group consisting of: xi) aromatic groups, wherein these aromatic groups may optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups, and xii) straight-chain, branched and cyclic aliphatic C1- to C1- groups. 12 - Groups, and xiii) Aromatic and aliphatic C1- to C 12 Combinations of - groups.

Description

Technical Field

[0001] The present invention relates to compounds, rubber mixtures containing the compounds, vehicle tires containing the rubber mixture in at least one component, methods for producing the compounds, and the use of the compounds as aging stabilizers and / or anti-ozone agents and / or dyes. Background Technology

[0002] Vehicle tires and industrial rubber products are known to use polymer materials, such as rubber in particular.

[0003] Under prolonged storage conditions, and especially in target applications that are typically at high temperatures, natural rubbers and synthetic polymers (such as IR, BR, SSBR, ESBR, etc.), as well as natural and synthetic oils, fats, and lubricants, undergo oxidation reactions, which adversely affect the original desired properties. Depending on the type of polymer, the polymer chains are shortened until the material liquefies or subsequently hardens.

[0004] Therefore, aging stabilizers play a decisive role in the durability of vehicle tires and other industrial rubber products.

[0005] Known aging stabilizers are aromatic amines, such as 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).

[0006] These molecules can react with oxygen or ozone or free radicals (such as alkyl, alkoxy, and alkyl peroxide radicals), thus scavenging them and protecting rubber and other materials from further oxidation.

[0007] However, a drawback of these substances is that they are suspected of being carcinogenic.

[0008] In particular, aging stabilizers that react with ozone and effectively remove ozone are also known as "ozone stabilizers". Summary of the Invention

[0009] The object of this invention is to provide a novel compound, particularly suitable for use as an aging stabilizer in automobile tires or other industrial rubber products, exhibiting significantly lower potential hazards and sufficient solubility in the appropriate matrix, for example and especially in polymers. This aims to ensure sustained optimal protection against oxygen and ozone, and to prevent the tendency to bloom, while reducing health hazards.

[0010] This objective is achieved by the compound of the present invention, by the rubber mixture of the present invention containing the compound, and by the vehicle tire of the present invention containing the rubber mixture of the present invention in at least one component.

[0011] This objective is further achieved by using the compound as an aging stabilizer and / or an anti-ozone agent.

[0012] The compounds according to the invention can be further used as dyes.

[0013] This objective is further achieved by the method according to the invention for producing the compound according to the invention.

[0014] The compounds according to the present invention have general formula I): I) , Where A is an aromatic group that may optionally have other substituents, and where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) Straight-chain, branched, and cyclic aliphatic C1-to-C 12 - Groups, and xiii) Aromatic and aliphatic C1-to-C 12 -A combination of groups, And R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group (wherein fluorine, bromine, and chlorine are preferred), a cyano group, an ester group, a ketone group, an ether group, and a thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

[0015] Preferably, A is an aromatic group that optionally has other substituents, and Where R 1 Selected from benzyl and straight-chain, branched and cyclic aliphatic C1- to C1- groups. 12 - A group composed of groups, and Where R 3 Select from the following groups: linear, branched, and cyclic aliphatic C1- to C1-C ... 12 - Groups, and aryl groups, cyano groups, halogen groups (of which fluorine, bromine and chlorine are preferred), ether groups and thioether groups, wherein n takes the value of 0 or 1 or 2 or 3 or 4, wherein when n is 2 or 3 or 4, these groups R 3 They are either identical or different from each other independently.

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

[0017] It is equally clear to those skilled in the art that (R 3 ) n The representation of bonds on the benzene ring in the indole structure should be understood to mean that these groups can each be arranged at any position on the benzene ring, excluding, of course, two or more (R) bonds. 3 At the same position, because the tetravalent nature of the carbon atom in the benzene ring has ruled out this possibility.

[0018] In the context of this invention, "C1-to-C" 12 The description of "-group" should be understood to mean a group having 1 to 12 carbon atoms. Without regard to this, "C1" is also used to describe the position of the carbon atom with the highest degree of oxidation / the carbon atom with the highest priority according to the Cahn-Ingold-Prelog convention (CIP). What this means in the appropriate context will be obvious to those skilled in the art.

[0019] The compound according to the invention is an indole derivative and exhibits a lower potential hazard compared to known aniline-based aging stabilizers (possible cleavage products of 6-PPD). Safety data sheets comparing the basic structures of aniline and indole show that, unlike aniline, indole is neither genotoxic nor mutagenic. This is a key advantage, especially in technical applications such as in vehicle tires or other rubber products, where rubber components are released through wear or other degradation processes. Furthermore, the oxidation products of 6-PPD pose a particular danger to coho salmon. Therefore, this should be considered applicable 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 for use in pharmaceutical or skin care compositions, as disclosed in US20200339581 A1 and JP 2004196699 A.

[0021] JP 06147585 B2 discloses indole derivatives having formula S1). S1) , In JP 06147585 B2, R 1 and R 2 The definition differs from that in this case.

[0022] Compared to indole derivatives from the prior art as shown in Formula S1), the compounds according to the present invention have the advantage of not containing vulcanizable groups (such as -SH) that allow bonding with rubber / polymers. Through bonding, the molecule will be locally bound and therefore may be ineffective at locations far from where oxidative stress occurs. Thus, bonding will prevent the molecule from exerting its full protective function as an aging stabilizer and / or anti-ozone agent.

[0023] This invention includes all advantageous embodiments, especially those embodied in the specification. The invention also includes embodiments resulting from combinations of different features with different levels of priority, such that the invention further includes combinations of a first feature described as "preferred" or, in cases of advantageous embodiments, as described with another feature, for example, described as "particularly preferred."

[0024] Preferably, A is selected from the group consisting of phenylene, naphthylene, and anthraceneyl groups, and phenylene, naphthylene, and anthraceneyl groups having one or more substituents, wherein the substituents are preferably selected from the group consisting of straight-chain, branched, and cyclic aliphatic C1- to C1-. 12 - Groups, aryl groups, cyano groups, halogen groups (of which fluorine, bromine and chlorine are preferred), ether groups and thioether groups.

[0025] Particularly preferred is that A is a phenylene group, and therefore a phenyl group having two or more bonded substituents. This results in particularly advantageous solubility of these compounds according to the invention in rubber blends, especially in rubber blends for vehicle tires and other industrial rubber products.

[0026] NHR groups on the indole group and the (phenylene) benzene ring 1 Ideally, the two sides should be arranged in a symmetrical configuration.

[0027] Preferably, the compound according to the invention has the structure of formula II): II) , Where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) Straight-chain, branched, and cyclic aliphatic C1-to-C 12 - group, and xiii) Aromatic and aliphatic C1-to-C 12 - A combination of groups, and where R 2Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group (wherein fluorine, bromine, and chlorine are preferred), a cyano group, an ester group, a ketone group, an ether group, and a thioether group, and Where m takes the value of 0, 1, 2, 3, or 4, and when m is 2, 3, or 4, these groups R 2 They are independently the same or different from each other, and Where R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group (wherein fluorine, bromine, and chlorine are preferred), a cyano group, an ester group, a ketone group, an ether group, and a thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

[0028] Similarly, when n is 0, 1, 2, or 4, the free positions on the benzene ring are hydrogen atoms.

[0029] It is equally clear to those skilled in the art that (R 2 ) m and R 1 The representation of HN bonds to the benzene ring should be understood as meaning that these groups can each be arranged at any position on the benzene ring, of course, not at the same position at the same time, because the tetravalent nature of the carbon atom in the benzene ring has ruled out this possibility.

[0030] Preferably, n is 0, which applies to equations I) and II).

[0031] Group R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups may optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups, and xii) Straight-chain, branched and cyclic aliphatic C1- to C1- 12 - Groups, and xiii) Aromatic and aliphatic C1-to-C 12 - A combination of functional groups.

[0032] The aromatic group from subgroup xi) is, for example, and preferably a phenyl group.

[0033] The aromatic groups of subgroup xi) may have substituents.

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

[0035] Preferably, the substituents are selected from the group consisting of ester groups, ketone groups, ether groups and thioether groups.

[0036] In a preferred embodiment, the aromatic group is not substituted on the two carbon atoms adjacent to the C1 atom (i.e., the carbon atoms bonded to the N atom). Given that the benzene ring is the basic structure, it is therefore preferable that the aromatic group is not substituted on the N atom. adjacent There are no substituents at the position.

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

[0038] R is preferred. 1 It is bonded to the nitrogen atom (N) via a tertiary carbon atom. Therefore, the C1 atom is preferably a tertiary carbon atom.

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

[0040] Compared to secondary and quaternary carbon atoms, the presence of this compound in rubber blends, particularly in rubber blends used in vehicle tires and other industrial rubber products, results in particularly good protective effects and thus exhibits optimal reactivity, especially in terms of mechanisms related to aging stabilization, in which undesirable side reactions are avoided.

[0041] Subgroup xiii) consists of a mixture of aromatic and aliphatic groups, for example and preferably selected from the group consisting of benzyl and 1-phenylalkyl groups having a total of 7 to 18 carbon atoms, particularly selected from benzyl and 1-phenylethyl groups, wherein the 1-phenylalkyl group, especially the 1-phenylethyl group, is particularly preferred due to the tertiary carbon atom.

[0042] R is particularly preferred. 1 It is a branched alkyl group having 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. Preferably, at least one branch exists on the C1 atom, that is, on the carbon atom bonded to the nitrogen atom (N), thus making the C1 atom a tertiary carbon atom.

[0043] R is a very special preferred option. 1 Selected from 1,3-dimethylbutyl and cyclohexyl groups, and particularly preferably R 1 It is a 1,3-dimethylbutyl group.

[0044] One or more groups R 2Independently identical or different from each other and selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group (where fluorine, bromine and chlorine are preferred), a cyano group, an ester group, a ketone group, an ether group and a thioether group.

[0045] By selecting appropriate starting materials, the listed groups R 2 Specifically, it can be bonded to the corresponding benzene ring / its precursor.

[0046] Preferably, m in equation II) is 0 (zero).

[0047] NHR groups on the indole group and the (phenylene) benzene ring 1 Ideally, the two sides should be arranged in a symmetrical configuration.

[0048] In a preferred embodiment, the compound has the structure of formula III): III) .

[0049] Compounds of Formula III) enable optimal antioxidant and therefore anti-aging protection, particularly in polymers. Furthermore, as mentioned above, compounds of Formula III pose significantly lower health risks than, for example, 6-PPD or other representatives of this class of substances.

[0050] The compounds of the present invention according to Formula I), Formula II), Formula III) and all the foregoing compounds are particularly suitable as aging stabilizers and / or ozone inhibitors in vehicle tires and / or industrial rubber products and / or oils and / or lubricants, such as air springs, bellows, conveyor belts, belts, drive belts, hoses, rubber belts, profiles, seals, membranes, tactile sensors for medical or robotic applications, or shoe soles or parts thereof.

[0051] Therefore, the present invention further provides the use of the compounds according to the invention as aging stabilizers and / or ozone inhibitors in vehicle tires and / or industrial rubber products and / or oils and / or lubricants, such as air springs, bellows, conveyor belts, belts, drive belts, hoses, rubber belts, profiles, seals, membranes, tactile sensors for medical or robotic applications, or shoe soles or parts thereof.

[0052] For the purpose of using compounds having formula I), formula II), formula III) and all of the foregoing compounds in the listed articles or substances, the compounds are used in and incorporated into the composition.

[0053] The composition is particularly a rubber blend used in vehicle tires or other industrial rubber products.

[0054] The present invention further provides the use of the compounds of the present invention having formulas I), II), and III) as well as all the foregoing compounds as dyes in fibers and / or polymers and / or paper and / or in (decorative) paints and coatings.

[0055] Another aspect of the present invention is a method for producing a compound having formula I), the method comprising the following steps: a) Provide a compound having formula A). A) ; b) Reacting a compound having formula A) with hydrogen gas or a hydride (especially a hydride) and a ketone or aldehyde (R 1 =O)(preferably a ketone, particularly and preferably methyl isobutyl ketone) reaction to give a compound having formula I). I) ; All of the above applies to group R. 1 and R 3 And n and A. It is also preferable that n is zero.

[0056] "Hydrogenating agent" should be understood to mean a compound that achieves hydrogenation. Such agents include hydrides, especially metal hydrides, as known to those skilled in the art.

[0057] Suitable hydrides include, for example, sodium borohydride.

[0058] In the context of this invention, hydrogen is not separately listed under "hydrogenating agent" because it is explicitly mentioned as an alternative. However, it should be understood that the term "hydrogenating agent" encompasses all agents that form hydrogen, which undergo hydrogenation in situ.

[0059] Preferably, the reaction in step b) with hydrogen (H2) and a ketone or aldehyde, preferably a ketone, uses a hydrogenation catalyst and is preferably carried out at a temperature of, for example, 50°C to 70°C, particularly 60°C. The reaction mixture is preferably subjected to hydrogen at a pressure of, for example, 15 to 25 bar, particularly 20 bar, and is preferably subsequently stirred for, for example, 1 to 20 hours, preferably 8 to 13 hours, particularly 10 hours.

[0060] The ketone in step b) is the subsequent group R. 1 It is a ketone derivative; in the case of aldehydes, it is correspondingly an aldehyde derivative.

[0061] For simplicity, the abbreviation R is used for aldehydes or ketones. 1 =O, because group R 1It is the portion that remains on the nitrogen atom after reacting with an aldehyde or ketone.

[0062] The preferred choice is ketone methyl isobutyl ketone.

[0063] Preferably, the method steps involving the reaction with hydrogen employ a suitable catalyst, referred to in the context of this invention as a "hydrogenation catalyst".

[0064] Preferably, the hydrogenation catalyst in this method is a noble metal catalyst, such as, in particular, palladium (Pd) or platinum (Pt). Preferably, the noble metal is used on carbon (C), such as palladium on carbon (Pd / C).

[0065] Alternatively, other known catalysts, such as Raney nickel or copper chromite, can be used.

[0066] Preferably, the reaction with hydrogen in step b) is carried out in a vessel suitable for relatively high pressure, such as, in particular, an autoclave or another pressure reactor.

[0067] In the above method, A is preferably a phenylene group and m is zero. The bonds on the benzene ring (of the phenylene group) are preferably in the para position to each other.

[0068] As described above, the present invention further provides a rubber compound.

[0069] The rubber mixtures according to the invention contain compounds having formula I), particularly having formula II), particularly having formula III). The rubber mixtures according to the invention can, in principle, be any rubber mixture, wherein the novel compounds of the invention having formula I), particularly having formula II), particularly having formula III), particularly acting as aging stabilizers and / or anti-ozone agents with low toxicity.

[0070] The rubber mixture of the present invention contains at least one type of rubber.

[0071] Preferably, the rubber compound 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 a compound having formula I), especially having formula II), especially having formula III).

[0072] The unit "phr" (parts per 100 parts by weight of rubber) used in this document is a standard indication of the amount of mixture formulations in the rubber industry. The dosage of these individual substances in parts by weight in this document is based on all high molecular weight (M) molecules present in 100 parts by weight of the mixture. w The total mass of rubber (greater than 20,000 g / mol).

[0073] In an advantageous embodiment of the invention, the rubber mixture according to the invention contains at least one diene rubber.

[0074] Therefore, rubber mixtures may contain diene rubber or mixtures of two or more different diene rubbers.

[0075] Diene rubber is a rubber formed by the polymerization or copolymerization of dienes and / or cyclic olefins, and therefore has C=C double bonds in the main chain or side groups.

[0076] The diene rubber is preferably selected from the group consisting of: 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, and a molecular weight M greater than 20,000 g / mol. w Liquid rubber, halogenated butyl 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.

[0077] Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halogenated butyl rubber, and / or ethylene-propylene-diene rubber are used particularly in the production of industrial rubber products such as belts, drive belts and hoses, and / or shoe soles. Preferably, mixtures of these rubbers are used, which are specific to those skilled in the art in terms of fillers, plasticizers, vulcanization systems, and additives.

[0078] The natural and / or synthetic polyisoprene in all embodiments can be cis-1,4-polyisoprene or 3,4-polyisoprene. However, cis-1,4-polyisoprene having a cis-1,4 content of >90% by weight is preferred. This polyisoprene can be obtained first by stereo-directional polymerization in solution with a Ziegler-Natta catalyst or using finely dispersed alkyl lithium. Secondly, natural rubber (NR) is such a cis-1,4-polyisoprene, wherein the cis-1,4 content in the natural rubber is greater than 99% by weight.

[0079] Further possibilities include mixtures of one or more natural polyisoprene and one or more synthetic polyisoprene.

[0080] In the context of this invention, the term "natural rubber" should be understood to mean naturally occurring rubber that can be obtained from the Hevea rubber tree and "non-Hevea" sources. Non-Hevea sources include, for example, the guayule shrub and dandelions such as TKS (Taraxacum kok-saghyz; Russian dandelion).

[0081] If the rubber compound of the present invention contains butadiene rubber (i.e., BR, polybutadiene), it can be of any type known to those skilled in the art. These include so-called high-cis types and low-cis types; polybutadiene having a cis content of not less than 90% by weight is called high-cis type, and polybutadiene having a cis content of less than 90% by weight is called low-cis type. An example of low-cis polybutadiene is Li-BR (lithium-catalyzed butadiene rubber) having a cis content of 20% to 50% by weight. Particularly good properties and low hysteresis of the rubber compound are achieved with high-cis BR.

[0082] One or more polybutadienes used can be end-group modified and / or functionalized along the polymer chain through modification and functionalization. Modification can be selected from modifications using hydroxyl and / or ethoxy and / or epoxy groups and / or siloxane groups and / or amino and / or aminosiloxane and / or carboxyl and / or phthalocyanine groups and / or silane-sulfide groups. However, other modifications known to those skilled in the art, also referred to as functionalization, are also useful. Metal atoms can be components of such functionalization.

[0083] When at least one styrene-butadiene rubber (styrene-butadiene copolymer) is present in the rubber mixture, this styrene-butadiene rubber may be selected from solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized styrene-butadiene rubber (ESBR), and a mixture of at least one SSBR and at least one ESBR is also acceptable. The terms "styrene-butadiene rubber" and "styrene-butadiene copolymer" are used synonymously in the context of this invention.

[0084] The styrene-butadiene copolymer used can be end-group modified and / or functionalized along the polymer chain through the modifications and functionalizations listed above for polybutadiene.

[0085] 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 halogenated butyl rubber.

[0086] In a particularly preferred embodiment of the 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).

[0087] In a particularly advantageous embodiment of the invention, the rubber compound comprises at least one natural polyisoprene (NR) and / or synthetic polyisoprene (IR), preferably in an amount of 50 to 100 phr, and in a particularly advantageous embodiment of the invention, in an amount of 80 to 100 phr, very particularly preferably 95 to 100 phr, and even more preferably 100 phr. Such a rubber compound exhibits particularly optimized tear and abrasion properties, as well as good processability and reversion stability.

[0088] If the rubber compound contains less than 100 phr of NR and / or IR, it preferably contains 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) as an additional rubber.

[0089] In another particularly advantageous embodiment of the invention, the rubber compound comprises at least one natural polyisoprene (NR), preferably in an amount of 5 to 55 phr, and in a particularly advantageous embodiment, in an amount of 5 to 25 phr, very particularly preferably 5 to 20 phr. This rubber compound exhibits particularly good processability and reversion stability, as well as optimal tear properties and optimal rolling resistance characteristics.

[0090] In another particularly advantageous embodiment of the invention, the rubber compound 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. This achieves particularly good tear and abrasion properties and optimal braking characteristics of the rubber compound according to the invention.

[0091] In another particularly advantageous embodiment of the invention, the rubber compound 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 a particularly advantageous embodiment of the invention, in an amount of 50 to 70 phr. This achieves particularly good rolling resistance characteristics of the rubber compound according to the invention. In a particularly advantageous embodiment of the invention, the SSBR is used in combination with at least one other rubber to achieve an optimal and balanced distribution of properties.

[0092] Preferably, the rubber compound contains at least one filler, in an amount preferably from 30 to 500 phr, particularly preferably from 50 to 400 phr, and even more preferably from 80 to 300 phr.

[0093] In an advantageous embodiment of the invention, the filler is preferably a reinforcing filler selected from the group consisting of carbon black and silicon dioxide.

[0094] Suitable carbon black includes any type of carbon black known to those skilled in the art. Preferably, the carbon black is selected from industrial carbon black and pyrolytic carbon black, with industrial carbon black being more preferred.

[0095] Preferably, the carbon black has an iodine value (also known as iodine adsorption value) according to ASTM D 1510 between 30 and 250 g / kg, preferably 30 to 180 g / kg, particularly preferably 40 to 180 g / kg, and very particularly preferably 40 to 130 g / kg, and a DBP value according to ASTM D2414 between 30 and 200 ml / 100 g, preferably 70 to 200 ml / 100 g, and particularly preferably 90 to 200 ml / 100 g.

[0096] The specific absorption volume of carbon black or light-colored filler with dibutyl phthalate is determined by the DBP value according to ASTM D 2414.

[0097] The use of this type of carbon black in rubber compounds (especially for vehicle tires) ensures the greatest possible trade-off between abrasion resistance and heat accumulation, which in turn affects eco-related rolling resistance.

[0098] Particularly suitable and preferred carbon blacks are those with an iodine adsorption value between 80 and 110 g / kg and a DBP value between 100 and 130 ml / 100 g, such as, in particular, type N339 carbon black.

[0099] The silica is preferably amorphous silica, such as precipitated silica, which is also called precipitated silica. However, pyrolytic silica can also be used alternatively, for example.

[0100] However, finely dispersed precipitated silica is particularly preferred, having a nitrogen surface area (BET surface area) of 35 to 400 m² / g, preferably 35 to 350 m² / g, more preferably 85 to 320 m² / g, and most preferably 120 to 235 m² / g (according to DIN ISO 9277 and DIN 66132), and a CTAB surface area of ​​30 to 400 m² / g, preferably 30 to 330 m² / g, more preferably 80 to 300 m² / g, and most preferably 115 to 200 m² / g (according to ASTM D 3765). This silica, for example, produces particularly good physical properties in rubber compounds used for tire treads. This also provides advantages in compound processing through reduced mixing time, while retaining the same product characteristics, leading to improved productivity. The silica used can therefore be, for example, silica of type Ultrasil® VN3 (trade name) from Evonik or highly dispersible silica known as HD silica (e.g. Zeosil® 1165 MP from Solvay).

[0101] In a particularly advantageous embodiment of the invention, the rubber compound contains at least one silica as a filler, preferably in an amount of 30 to 500 phr, particularly preferably 50 to 400 phr, and even more preferably 80 to 300 phr.

[0102] In these quantities, silica is present, in particular, as the sole or primary filler (based on a total filler content of more than 50% by weight).

[0103] In a further advantageous embodiment of the invention, the rubber compound contains at least one silica as an additional filler, preferably in an amount of 5 to 100 phr, particularly preferably 5 to 80 phr, and even more preferably 10 to 60 phr.

[0104] In these quantities, silica is present in particular as an additional filler, in addition to another major filler, such as carbon black.

[0105] The terms “silicic acid” and “silica” are used synonymously in the context of this invention.

[0106] In a particularly advantageous embodiment of the invention, the rubber compound according to the invention contains at least one carbon black in amounts of 0.1 to 60 phr, preferably 3 to 40 phr, particularly preferably 5 to 30 phr, and very particularly preferably 5 to 15 phr. In these amounts, carbon black is present, in particular, as an additional filler, in addition to the main filler, such as silica in particular.

[0107] In another advantageous embodiment of the invention, the rubber compound according to the invention contains at least one carbon black in amounts of 30 to 300 phr, preferably 30 to 200 phr, particularly preferably 40 to 100 phr. In these amounts, the carbon black is present as the sole or primary filler, and therefore optionally in combination with silica in the aforementioned smaller amounts.

[0108] In a particularly advantageous embodiment of the invention, the rubber compound contains at least one carbon black at 5 to 60 phr, particularly preferably 5 to 40 phr, and at least one silica at 50 to 300 phr, preferably 80 to 200 phr.

[0109] Rubber compounds may contain additional fillers, either reinforcing or unreinforcing.

[0110] In the context of this invention, other (non-reinforcing) fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide, or rubber gels, as well as fibers (e.g., aramid fibers, glass fibers, carbon fibers, cellulose fibers).

[0111] In addition, optional reinforcing fillers include, for example, carbon nanotubes (CNTs, including discrete CNTs, hollow carbon fibers (HCFs) and modified CNTs containing one or more functional groups (such as hydroxyl, carboxyl and carbonyl groups), graphite and graphene, as well as so-called “carbon-silicon biphase fillers”.

[0112] In the context of this invention, zinc oxide is not included in the filler.

[0113] The rubber compound may further contain conventional additives in conventional parts by weight, preferably added during at least one primary mixing stage in the production of the compound. These additives include... a) Aging stabilizers known in the prior art, Examples include 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'-xylyl-p-phenylenediamine (DTPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD), and N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD). Or dihydroquinoline, 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 used for binders and fillers, particularly carbon black or silica, such as S-(3-aminopropyl)thiosulfate and / or its metal salts (for carbon black binders) and silane coupling agents (for silica, particularly silica binders). d) Anti-ozone wax, e) Resins, especially tackifying resins, f) Plasticizing aids, such as 2,2'-dibenzoylaminodiphenyl disulfide (DBD), and g) Processing aids, such as fatty acid esters and metal soaps, particularly zinc and / or calcium soaps. h) Plasticizers, such as, in particular, aromatic, naphthenic or paraffinic mineral oil plasticizers, such as MES (mild extraction solvate) or RAE (residual aromatic extract) or TDAE (treated distillate aromatic extract), or rubber-based liquid oil (RTL) or biomass-based liquid oil (BTL) preferably having a polycyclic aromatic hydrocarbon content of less than 3% by weight according to method IP 346, or triglycerides, such as rapeseed oil or ointment or hydrocarbon resin or liquid polymer (whose average molecular weight (determined by GPC = gel permeation chromatography according to BS ISO 11344:2004) is between 500 and 20,000 g / mol).

[0114] When using mineral oil, it is preferably selected from the group consisting of: DAE (distillate aromatic extract), RAE (residual aromatic extract), TDAE (treated distillate aromatic extract), MES (mild extracted solvent), and naphthenic oil.

[0115] In particularly advantageous embodiments, the rubber mixtures according to the invention do not contain aging stabilizers from the group consisting of p-phenylenediamine, particularly those listed in a) above, except for the compounds of formula I), especially formula II) and / or III). In particularly preferred embodiments, the rubber mixtures according to the invention contain, in particular, 0 to 0.1 phr, especially 0 phr, of additional aging stabilizers based on p-phenylenediamine and selected from the group consisting of: 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'-xylyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), and N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD).

[0116] The use of very small amounts of p-phenylenediamine, preferably 0 to 0.1 phr, and particularly preferably 0 phr, and compounds having formula I), especially formula II), especially formula III), according to the invention, enables comparable protective effects with lower toxicity. The compounds of the present invention having formula I), especially formula II), especially formula III), replace the p-phenylenediamines listed in the prior art.

[0117] In a further advantageous embodiment of the invention, at least one other representative of the listed p-phenylenediamine aging stabilizers is present, and thus the compounds according to the invention only partially replace p-phenylenediamine known in the prior art. This also achieves the advantages of the invention, albeit not to the optimal degree.

[0118] In advantageous embodiments, in addition to the compounds of formula I) of the present invention, an aging stabilizer based on dihydroquinoline (such as TMQ) is present in the rubber mixture. The amount of dihydroquinoline (especially TMQ) present is preferably 0.1 to 3 phr, particularly 0.5 to 1.5 phr.

[0119] Anti-ozone waxes (group d above) are considered separately and are present in the rubber mixture in a preferred embodiment of the invention, regardless of the presence of additional aging stabilizers (a).

[0120] The silane coupling agent can be any type known to those skilled in the art.

[0121] Furthermore, one or more different silane coupling agents can be used in combination with each other. Therefore, rubber compounds can contain mixtures of different silanes.

[0122] During the mixing (in situ) of rubber / rubber mixtures or even in the context of pretreatment (pre-modification) before the addition of fillers to the rubber, silane coupling agents react with surface silanol groups or other polar groups of silica, particularly silica.

[0123] Coupling agents known from the prior art are bifunctional organosilanes, which have at least one alkoxy, cycloalkoxy, or phenoxy group as a leaving group on a silicon atom and a group as another functional group that may, upon cleavage, participate in a chemical reaction with the double bond of the polymer. This latter group may, for example, include the following chemical groups: -SCN, -SH, -NH2, or -S x - (where x = 2 to 8).

[0124] Therefore, suitable silane coupling agents include, for example, 3-mercaptopropyltriethoxysilane, 3-thiocyanopropyltrimethoxysilane, or 3,3'-bis(triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms, such as 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT), the corresponding disulfide (TESPD), or other sulfides having 1 to 8 sulfur atoms mixed with various sulfides in different amounts. TESPT can also be added, for example, as a mixture with carbon black (from Evonik's trade name X50S®).

[0125] Terminally capped mercaptosilanes, such as those known, for example, by WO 99 / 09036, can also be used as silane coupling agents. Silanes described in WO 2008 / 083241 A1, WO 2008 / 083242 A1, WO 2008 / 083243 A1, and WO 2008 / 083244 A1 can also be used. Permissible silanes include, for example, those marketed by Momentive, USA, in many variations under the name NXT, such as, in particular, 3-octanoylthio-1-propyltriethoxysilane, or those marketed by Evonik Industries under the name VP Si 363®.

[0126] The total proportion of other additives is preferably 3 to 150 phr, more preferably 3 to 100 phr, and most preferably 5 to 80 phr.

[0127] Zinc oxide (ZnO) can be included in the total proportion of other additives in the above-mentioned amounts.

[0128] This can be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder. Conventionally used zinc oxide typically has a BET surface area of ​​less than 10 m² / g. However, it is also possible to use zinc oxide with a BET surface area of ​​10 to 100 m² / g, such as so-called "nano zinc oxide."

[0129] The rubber mixtures of the present invention are preferably used in vulcanized form, particularly in vehicle tires or other vulcanized industrial rubber products.

[0130] The terms “vulcanized” and “crosslinked” are used synonymously in the context of this invention.

[0131] The vulcanization of the rubber mixtures of the present invention is preferably carried out in the presence of sulfur and / or a sulfur donor by means of a vulcanization accelerator, some of which can also act as sulfur donors. The accelerators are selected from the group consisting of: thiazole accelerators, mercapto-containing accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate ester accelerators, and guanidine accelerators.

[0132] Preferred accelerators are those selected from the group consisting of: N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazole-2-sulfenamide (MBS), N-tert-butyl-2-benzothiazole sulfenamide (TBBS), and guanidine accelerators (such as diphenylguanidine (DPG)).

[0133] The sulfur donor used can be any sulfur donor known to those skilled in the art.

[0134] Vulcanization retarders can also be present in rubber compounds.

[0135] The production of the rubber compound according to the invention is preferably carried out additionally by methods conventional in the rubber industry, including the initial production in one or more mixing stages of a primary mixture containing all components except for the vulcanization system (e.g., sulfur and substances that affect vulcanization). The final mixture is produced by adding the vulcanization system in the final mixing stage.

[0136] For example, the final mixture can be further processed and shaped into a suitable form by means of extrusion or calendering.

[0137] The rubber compound according to the invention is particularly suitable for vehicle tires, especially pneumatic vehicle tires. In principle, its use in all tire components, particularly in external components, especially and preferably in the flange profile, tread, and / or sidewall. In the case of a tread having a crown / base configuration, the rubber compound according to the invention is preferably used at least in the crown.

[0138] For use in vehicle tires, the mixture is made into the appropriate shape (preferably for external parts) as a final mixture before vulcanization and is applied in a known manner during the production of the vehicle tire.

[0139] As described above, the production of the rubber compound according to the invention is carried out, which is used as any other body compound in vehicle tires. The difference lies in the shaping after the extrusion / calendering of the compound. The shape of the undulcanized rubber compound thus obtained for one or more different carcass compounds is then used in the construction of the green tire.

[0140] Here, "body mixture" refers to the rubber mixture used for the internal components of a tire, such as primarily rubber rollers, liner (inner layer), bead profile, belt, tire shoulder, belt profile, tire carcass, bead reinforcement, bead profile, flange profile, and hoops.

[0141] The uncured green tires were then cured.

[0142] In order to use the rubber compound of the present invention in drive belts and other belts, especially in conveyor belts, the extruded, uncured compound is shaped appropriately and is typically provided simultaneously or subsequently with strength members, such as synthetic fibers or steel cords. This generally provides a multilayer construction consisting of one and / or more layers of rubber compound, one and / or more layers of the same and / or different strength members, and one and / or more additional layers of the same and / or another rubber compound.

[0143] The present invention further provides a vehicle tire comprising, in at least one component, a rubber compound according to the invention, the rubber compound containing a compound according to the invention.

[0144] The vulcanized vehicle tire contains at least one vulcanized rubber of the rubber mixture of the present invention in at least one component. Those skilled in the art know that most substances (e.g., existing rubbers) are already present in a chemically modified form after mixing or only after vulcanization, or may be present in a chemically modified form.

[0145] In the context of this invention, "vehicle tire" should be understood to mean pneumatic tires and solid rubber tires for vehicles, including tires for industrial and construction site vehicles, trucks, automobiles, and two-wheeled vehicle tires.

[0146] Preferably, the vehicle tire according to the invention contains the rubber compound according to the invention in at least one external component, wherein the external component is preferably a tread, sidewall, and / or flange profile.

[0147] Therefore, the vehicle tire according to the invention may contain, in several components, a rubber compound according to the invention in a suitable composition, the rubber compound containing compounds of the invention having formula I), particularly having formula II), particularly having formula III). Detailed Implementation

[0148] The invention will now be described in more detail with reference to working examples.

[0149] The following are preferred embodiments of compounds having formula I) or II), such as compounds having formula III), as shown in formula XI): XI) .

[0150] 5.40 g (25.9 mmol, 1 equivalent) of 2-(4-aminophenyl)-1H-indole, 1.09 g of platinum carbon (Pt / C) (5%) (0.2 g on 4.67 mmol substrate), and 50.0 mL of methyl isobutyl ketone (MIBK) were weighed into a Teflon-lined stainless steel autoclave. The reaction mixture was then subjected to hydrogen at 20 bar and stirred at 60°C for 10 hours. After termination of the reaction, excess hydrogen was released, and the suspension was passed through a Celite filter. ® Filter and wash with ethanol. Evaporate the filtrate to dryness and dry under vacuum. Recrystallize it from cyclohexane. Give a light gray to purple solid; yield 5.40 g (71% of theoretical value).

[0151] 1 H-NMR (nuclear magnetic resonance) (500 MHz, DMSO- d6 ) δ = 11.16 (s, 1H), 7.56 (d, J =8.6 Hz, 2H), 7.43 (dd, J = 7.7, 1.1 Hz, 1H), 7.32 (dd, J = 7.9, 1.0 Hz, 1H), 7.00(ddd, J = 8.1, 7.0, 1.2 Hz, 1H), 6.93 (ddd, J = 8.0, 7.0, 1.1 Hz, 1H), 6.63 (d, J =8.6 Hz, 2H), 6.57 (d, J = 1.4 Hz, 1H), 5.56 (d, J = 8.5 Hz, 1H), 3.56 - 3.47 (m,1H), 1.74 (dt, J = 13.5, 6.7 Hz, 1H), 1.47 (dt, J = 13.9, 7.1 Hz, 1H), 1.25 (dt, J = 13.5, 6.9 Hz, 1H), 1.11 (d, J = 6.2 Hz, 3H), 0.93 (d, J = 6.6 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H).

[0152] 13C-NMR (126 MHz, 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 oxidation induction time (OIT) Under laboratory conditions, the potential protective effect of compounds with formula III) as aging stabilizers was investigated by measuring oxidation induction time.

[0156] Therefore, compounds having formula III) and 6-PPD were combined in each case with polymers (liquid-synthesized polyisoprene (IR), LIR-50, Kuraray, with weight-average molecular weight distribution M). w = 54,000 g / mol, glass transition temperature T g = -63°C) together were heated at a constant temperature (180°C) until oxidation began (initial temperature 35°C, heated to 170°C at a heating rate of 20 K / min, then heated to 180°C at a heating rate of 1 K / min; purge gas: nitrogen (N2), volumetric flow rate 50 mL / min). The sample was held isothermally at 180°C for 5 minutes under N2 atmosphere, and then the atmosphere was switched to O2 atmosphere (volumetric flow rate 50 mL / min).

[0157] Oxidation was determined by peaks using DSC (Differential Scanning Calorimetry).

[0158] Measure the oxidation time (in minutes).

[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 with formula III) is a suitable alternative to the more harmful compound 6-PPD.

[0162] For use in rubber compounds for vehicle tires, during the production of the rubber compound, in a manner known to those skilled in the art, for example, replacing aging stabilizers known to those skilled in the art, such as 6PPD, 7PPD, or IPPD, the compound of the present invention having formula I), or for example having formula III), is added in one of the mixing stages.

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

[0164] For comparison, rubber compound V1 contains 6 PPD in place of the compound having formula III) as an aging stabilizer, with the rest of the composition being the same. The quantities in Table 2 are expressed in phr.

[0165] According to methods commonly used in the rubber industry, the mixture is produced in three stages under standard conditions in a laboratory mixer with a volume of 300 ml to 3 liters. Initially, in the first mixing stage (preliminary mixing stage), all components except the vulcanization system (sulfur and vulcanization-affecting substances) are mixed at 145°C to 165°C (target temperature 152°C to 157°C) for 200 to 600 seconds. In the second stage, the mixture from the first stage is mixed again. In the third stage (final mixing stage), the vulcanization system is added to obtain the final mixture, which is then mixed at 90°C to 120°C for 180 to 300 seconds.

[0166] After t95 to t100 (measured using a moving die rheometer according to ASTM D 5289-12 / ISO 6502), test samples are produced from all mixtures by vulcanization under pressure at 160°C to 170°C. In addition, a portion of the test samples from both V1 and E1 were aged (in air at 70°C for 28 days).

[0167] The following typical material properties for the rubber industry were determined for all tested samples: • Resilience at room temperature (RT) according to ISO 4662 or ASTM D 1054 • According to DIN 53 504, the stress value (M 300) at 300% elongation at room temperature (RT) and the elongation at break. For V1 and E1, determine the difference between the values ​​of the unaged sample and the aged sample.

[0168] The V1 values ​​obtained in each case are standardized to 100% for reference.

[0169] The obtained E1 value (the difference between unaged and aged) is reported as a performance percentage relative to the corresponding V1 reference value, where values ​​above 100% are favorable. As can be clearly seen from Table 2, the compounds of the present invention having Formula III, which are representative of compounds having Formula I), result in improved aging stability because important properties of E1 after aging, such as stress value at 300% elongation (300 modulus), elongation at break, and resilience, are at a higher level than V1 in each case.

[0170] Table 2 Element V1 E1 IR 100 100 Carbon Black N 339 50 50 MES 8 8 6PPD 2 - Compounds having formula III) - 2 ZnO 3 3 stearic acid 2 2 TBBS 1.2 1.2 sulfur 1.2 1.2 characteristic M300 100 128 Elongation at break 100 105 Rebound elasticity under RT 100 106

Claims

1. A rubber compound comprising a compound having formula I), The compound having formula I) is: I) ， Where A is an aromatic group that may optionally have other substituents, and where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) Straight-chain, branched, and cyclic aliphatic C1-to-C 12 - group, and xiii) Aromatic and aliphatic C1-to-C 12 -A combination of groups, And R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group, cyano group, ester group, ketone group, ether group, and thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

2. The rubber mixture according to claim 1, wherein the rubber mixture contains at least one diene rubber.

3. The rubber mixture according to claim 2, wherein the at least one diene rubber is 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 halogenated butyl rubber.

4. The rubber mixture according to claim 1, characterized in that, The halogen group is selected from fluorine, bromine and chlorine.

5. A compound having formula I): I) ， Where A is an aromatic group that may optionally have other substituents, and where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) branched and cyclic aliphatic C1-to-C 12 - group, and xiii) Aromatic and aliphatic C1-to-C 12 - A combination of groups, where R 1 It bonds to the nitrogen atom (N) via a tertiary carbon atom. And R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group, cyano group, ester group, ketone group, ether group, and thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

6. The compound according to claim 5, characterized in that, A is selected from the group consisting of phenylene, naphthylene, and anthraceneylene groups, and phenylene, naphthylene, and anthraceneylene groups having one or more substituents, wherein these substituents are selected from the group consisting of straight-chain, branched, and cyclic aliphatic C1- to C2-chain groups. 12 - Groups, and aryl groups, cyano groups, halogen groups, ether groups and thioether groups.

7. The compound according to claim 5, characterized in that, It has the structure of formula II): II) , Where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) Straight-chain, branched, and cyclic aliphatic C1-to-C 12 - group, and xiii) Aromatic and aliphatic C1-to-C 12 -A combination of groups, And R 2 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group, a cyano group, an ester group, a ketone group, an ether group, and a thioether group, and Where m takes the value of 0, 1, 2, 3, or 4, and when m is 2, 3, or 4, these groups R 2 They are independently the same or different from each other, and the group R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group, cyano group, ester group, ketone group, ether group, and thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

8. The compound according to any one of claims 5 to 7, characterized in that, The halogen group is selected from fluorine, bromine and chlorine.

9. The compound according to claim 5, characterized in that, n is 0.

10. The compound according to claim 5, characterized in that, R 1 It is a branched alkyl group having 3 to 12 carbon atoms.

11. The compound according to claim 10, characterized in that, R 1 It is a branched alkyl group having 3 to 8 carbon atoms.

12. The compound according to claim 5, characterized in that, R 1 Selected from 1,3-dimethylbutyl and cyclohexyl groups.

13. The compound of claim 12, characterized in that, R 1 It is a 1,3-dimethylbutyl group.

14. The compound according to claim 7, characterized in that, m is 0 (zero).

15. The compound according to claim 5, characterized in that, It has the structure of formula III): III) 。 16. The use of a compound having formula I) as an aging stabilizer in vehicle tires or industrial rubber products and / or oils and / or lubricants, The compound having formula I) is: I) ， Where A is an aromatic group that may optionally have other substituents, and where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) Straight-chain, branched, and cyclic aliphatic C1-to-C 12 - group, and xiii) Aromatic and aliphatic C1-to-C 12 -A combination of groups, And R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group, cyano group, ester group, ketone group, ether group, and thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

17. Use of the compound having formula I) as described in claim 16, characterized in that, These industrial rubber products include air springs, bellows, conveyor belts, belts, transmission belts, hoses, rubber belts, profiles, seals, membranes, tactile sensors for medical or robotic applications, or shoe soles or their components.

18. The use of a compound having formula I) as a dye in fibers and / or polymers and / or paper and / or in paints and coatings, The compound having formula I) is: I) ， Where A is an aromatic group that may optionally have other substituents, and where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) Straight-chain, branched, and cyclic aliphatic C1-to-C 12 - group, and xiii) Aromatic and aliphatic C1-to-C 12 -A combination of groups, And R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group, cyano group, ester group, ketone group, ether group, and thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

19. Use of the compound having formula I) as described in claim 18, characterized in that, The paint in question is a decorative paint.

20. A method for producing a compound having formula I), the method comprising the following steps: a) Provide a compound having formula A). A) ； b) Reacting the compound having formula A) with hydrogen or a hydride and a ketone or aldehyde to obtain the compound having formula I). I) ， Where A is an aromatic group that may optionally have other substituents, and Where R 1 Choose from the following groups: xi) Aromatic groups, wherein these aromatic groups optionally have substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups. (and xii) Straight-chain, branched, and cyclic aliphatic C1-to-C 12 - group, and xiii) Aromatic and aliphatic C1-to-C 12 - A combination of groups, and where R 3 Selected from the group consisting of: linear, branched, and cyclic saturated and unsaturated aliphatic C1- to C2- groups, optionally with one or more halogen substituents. 12 - A group, optionally an aryl group having one or more halogen substituents, and a halogen group, cyano group, ester group, ketone group, ether group, and thioether group, wherein n takes the value of 0, 1, 2, 3, or 4, wherein when n is 2, 3, or 4, these groups R 3 They are either identical or different from each other independently.

21. The method as described in claim 20, characterized in that, The halogen group is selected from fluorine, bromine and chlorine.

22. The method as described in claim 20, characterized in that, The reaction in step b) with hydrogen (H2) and the ketone or aldehyde is carried out using a hydrogenation catalyst and at a temperature of 50°C to 70°C, and subjected to hydrogen at a pressure of 15 to 25 bar, and the reaction is carried out in an autoclave or in another pressure reactor.

23. The method according to any one of claims 20 to 22, characterized in that, In step b), the compound having formula A) is reacted with a ketone.

24. A vehicle tire comprising, in at least one component, the rubber compound as claimed in claim 1.

25. The vehicle tire as claimed in claim 24, characterized in that, The component is an external component.

26. The vehicle tire as claimed in claim 25, Its features are, The external components are the tread, sidewall, and / or flange profiles.

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