Compound for use as Anti-aging agent in rubber blends, and vehicle tire

Abstract

The invention relates to a compound of formula (I), which is defined in more detail in the present text, a rubber blend containing the compound, a vehicle tire comprising the rubber blend in at least one component, a process for preparing the compound, and the use of the compound as an anti-aging agent and / or antioxidant.

Description

[0001] Description

[0002] Compound as an ageing inhibitor in rubber compounds and

[0003] vehicle tires

[0004] The invention relates to a compound of formula (I)

[0005] (I), which is further defined in the present text, a rubber mixture comprising this compound, a vehicle tire which has the rubber mixture in at least one component, a process for preparing this compound and the use of the compound as an ageing inhibitor and / or antioxidant.

[0006] It is known that polymeric compounds, particularly rubbers, are used in vehicle tires and rubber articles other than vehicle tires (preferably technical rubber articles). Natural rubber (NR), synthetic polymers (e.g., IR, BR, SSBR, ESBR, etc.), as well as natural and synthetic oils, greases, lubricants, and fuels, are subject to oxidation reactions during extended storage, often in their intended application, which often takes place at elevated temperatures. These oxidation reactions adversely affect the originally desired properties. Depending on the type of polymeric or long-chain compound, these oxidation reactions are shortened (even leading to liquefaction of the article) or a subsequent, undesirable hardening of the material or article occurs.

[0007] Anti-aging agents therefore make a significant contribution to improving the longevity of vehicle tires and rubber articles and corresponding compositions. Typical anti-aging agents are aromatic amines, such as 6PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine), IPPD (N-isopropyl-N'-phenyl-p-phenylenediamine) or SPPD (N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine). These compounds and anti-aging agents in general can react with oxygen, ozone and / or radicals, preferably alkyl, alkoxy and alkylperoxy radicals, and capture them, thus protecting the polymeric or long-chain compounds from particularly undesirable oxidation and radical reactions. Anti-aging agents that react with or capture ozone are often also specifically called "ozone protectants" or "antiozonants".

[0008] The disadvantage of the above-mentioned compounds, however, is the suspicion that they could be carcinogenic and / or harmful to the environment.

[0009] Another problem associated with anti-aging agents is undesirable blooming. Due to their poor solubility in the surrounding polymer matrix of the tire or rubber article, molecules of the anti-aging agent diffuse onto the surface of the tire or rubber article, often forming a film there whose color is usually distinguishable from the rest of the article. In vehicle tires, this typically manifests itself in a brown discoloration of the otherwise black sidewall. In addition to the aesthetic disadvantages, this also has disadvantages with regard to the anti-aging effect. Typically, bloomed compounds are removed or extracted from the vehicle tire through this process. This not only reduces the total amount of anti-aging agent, but also causes additional molecules of the anti-aging agent to diffuse towards the surface, thus further reducing the protective effect.

[0010] Antiaging agents in rubber compositions are, of course, known. For example, JP 6049236 B2 discloses phosphorus-containing antiaging agents.

[0011] The invention is based on the object of providing novel compounds that can be used, in particular, as anti-aging agents in vehicle tires and / or other rubber articles other than vehicle tires, preferably technical rubber articles, with a lower hazard potential and sufficient solubility in the respective matrix, for example and in particular in the polymer. This is intended to ensure continued optimal protection against oxygen, radicals, and / or (preferably) ozone while reducing health hazards, and to minimize or even prevent the tendency toward blooming.

[0012] At the same time, the compound is intended to achieve an anti-aging effect that is at least sufficiently equivalent to that of known aromatic amines, such as 6PPD.

[0013] The object is achieved by the compound according to the invention according to formula (I):

[0014] (I), where

[0015] - R 1 is selected from the group consisting of

[0016] - xi) aromatic residues, and

[0017] - xii) aliphatic C3 to C12 residues,

[0018] - R 2 and R 3 are the same or different and are independently selected from the group consisting of aliphatic Ci to Ci2 residues, aromatic residues, halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether residues,

[0019] - R 4is selected from the group consisting of aliphatic Ci to C2o residues and aromatic Cs to C2o residues, - X is oxygen or sulfur, preferably oxygen,

[0020] - m is 0 or 1 or 2 or 3, and

[0021] - n is 0 or 1 or 2 or 3 or 4.

[0022] The compound of formula (I) according to the invention is a phenophosphazinine derivative and has a potentially lower hazard potential than known anti-aging agents based on aniline and its degradation products, as initial studies on related compounds seem to suggest (Yin Zhi Gang et al. Dyes and Pigments, 2009, 81 (2), 137-143). This is a decisive advantage in vehicle tires and rubber articles other than vehicle tires (preferably technical rubber articles), since the rubber ingredients are often released through abrasion or other degradation processes.

[0023] The compound of formula (I) according to the invention has, in particular compared to the known and customary anti-aging agent 6PPD, an at least comparable or sufficiently similar anti-aging effect (see examples below), in particular in rubber mixtures or vehicle tires.

[0024] Preferably, the compound of formula (I) according to the invention is an antiozonant, particularly preferably additionally an antiozonant, ie in addition to the ability to react with oxygen and / or radicals (preferably as mentioned above).

[0025] The compound of formula (I) according to the invention is preferably suitable as a replacement for 6PPD, the degradation products of which are particularly demonstrably toxic to silver salmon and thus probably also to other aquatic organisms.

[0026] The indices m and n describe the number of corresponding groups R 2 and R 3. If m or n is 0 (zero), the residues R 2 or R 3 are not present and are instead replaced by a hydrogen atom. This is preferably the case independently of each other. Preferably, R 2 and R 3 optional in the compounds according to the invention.

[0027] It is also clear to the person skilled in the art that the representation of the links of (R 2 )m and NHR 1 to the 4 possible carbons in the corresponding 6-membered ring and (R 3 )n to all possible carbon atoms in the neighboring ring. These groups are located at any position in the ring assigned to them, except, of course, two or more at the same time. In the context of the present invention, the radical NHR 1 synonymous with N(H)R 1 . It means it is a secondary amine.

[0028] In the context of the present invention, the term “C3 to C12 residues” means a residue comprising 3 to 12 carbon atoms.

[0029] In the context of the present invention, the general principle is that the invention is not intended to be tied to a specific mechanism of action or a specific explanation.

[0030] The compound of formula (I) according to the invention has sufficient to very good solubility in rubber mixtures, in particular for vehicle tires and rubber articles other than vehicle tires (in particular technical rubber articles). The solubility is preferably achieved by suitable selection of the radicals R 2 , R 3 and / or R 4This minimizes or even largely prevents unwanted blooming of this compound, which in turn is beneficial for the anti-aging effect. The less blooming of the anti-aging agent, the less is lost intentionally or unintentionally through the surface, and the less anti-aging agent diffuses back into the coating. This also has significant environmental benefits.

[0031] The invention encompasses all preferred embodiments, which are reflected, among other things, in the patent claims. In particular, the invention also encompasses and is deemed to disclose embodiments that result from the combination of different features (even with different degrees of preference for these features), so that a combination of a first feature designated as "preferred" with a second feature designated, for example, as "particularly preferred" is also encompassed and disclosed by the invention.

[0032] Furthermore, all statements regarding the features of the compounds according to the invention also apply to the process according to the invention for producing the compounds, the rubber mixture according to the invention containing the compounds, and the use according to the invention. The compound according to the invention:

[0033] A compound according to the invention is preferred, wherein it has the structure according to

[0034] Formula (II) has:

[0035] (II), where R 1 , R 2 , R 3 , R 4 , X, m, and n are as defined in claim 1, preferably as described in the text as preferred.

[0036] In the context of the present invention, X is oxygen (ie, O) or sulfur (ie, S). Particularly preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein X is oxygen.

[0037] What is said in this text regarding the compound of formula (I) particularly preferably also applies, mutatis mutandis, to the compound of formula (II), and vice versa. A compound of formula (II) solves the problem underlying the invention particularly well and exhibits sufficient to good solubility in rubber mixtures, especially for vehicle tires.

[0038] Particularly preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein n and m are identical or different, preferably identical.

[0039] Preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein n and m are zero.

[0040] In the context of the present invention, R 2 and R 3 are fundamentally independent of each other. In the compound according to the invention, preferably as described above and / or below as preferred, the radicals R 2 and R 3 identical or different and independently selected from the group consisting of aliphatic Ci to Ci2 residues, aromatic residues, halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether residues.

[0041] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aliphatic Ci to Ci2 radicals in R 2 and R 3 independently of one another comprise linear partial residues, branched partial residues and / or cyclic partial residues; are preferably linear, branched or cyclic.

[0042] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aliphatic Ci to Ci2 radicals in R 2 and R 3 are independently saturated or unsaturated, preferably saturated.

[0043] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aliphatic radicals in R 2 and R 3are aliphatic Ci to Cw radicals, preferably aliphatic Ci to Cs radicals, more preferably aliphatic Ci to Ce radicals, particularly preferably aliphatic Ci to C4 radicals, very particularly preferably aliphatic Ci to C2 radicals, preferably methyl and / or ethyl.

[0044] In some cases, a compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aliphatic Ci to Ci2 radicals in R 2 and R 3 independently comprise one or more than one halogen substituent, preferably selected from the group consisting of fluorine, chlorine and bromine.

[0045] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aromatic radicals in R 2 and R 3independently of one another comprise 5 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, particularly preferably 8 to 10 carbon atoms, most preferably 6 to 8 carbon atoms.

[0046] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aromatic radicals in R 2 and R 3 independently comprise one or more than one halogen substituent, preferably selected from the group consisting of fluorine, chlorine and bromine.

[0047] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the halogen radicals in R 2 and R 3 are independently selected from the group consisting of fluorine, chlorine and bromine.

[0048] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the ester residues, ketone residues, ether residues and thioether residues in R 2 and R 3 independently comprise 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 9 carbon atoms, even more preferably 1 to 7 carbon atoms, most preferably 1 to 5 carbon atoms. In some cases, it is preferred that the above upper limits of carbon atoms are combined with at least 2 carbon atoms as the lower limit.

[0049] Preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein R 2 and R 3independently of one another comprise a maximum of 12 carbon atoms, preferably 10 carbon atoms, particularly preferably 6 carbon atoms, most preferably 4 carbon atoms. This means, for example, that R 3 comprises a maximum of 10 carbon atoms, while R 2 contains a maximum of 6 carbon atoms.

[0050] The mentioned residues R 2 and R 3 are particularly preferably already connected by selecting suitable starting compounds.

[0051] The number and type of substituents R 2 or R 3 When selected appropriately, it has a decisive influence on the solubility of the compound according to the invention within the rubber mixture according to the invention and the vehicle tires according to the invention. This preferably also applies, in addition or alternatively, to R 4 to.

[0052] The rest R 4is selected from the group consisting of aliphatic C1 to C2o residues and aromatic C5 to C2o residues. A compound according to the invention, preferably as described above and / or below as preferred, is preferred, wherein R 4 is an aromatic Cs to C residue, preferably an aromatic Cs to Cis residue, more preferably an aromatic Cs to Cu residue, particularly preferably an aromatic Ce to Ci2 residue, most preferably an aromatic Ce to Cw residue.

[0053] The aromatic Cs to C2o radical is particularly preferred, phenyl or benzyl.

[0054] Preferred is a compound according to the invention wherein R 4is an aliphatic C1 to C2 radical, preferably an aliphatic C2 to C3 radical, more preferably an aliphatic C3 to C8 radical, particularly preferably an aliphatic C1 to C2 radical, most preferably an aliphatic C5 to C8 radical. This preferably applies alternatively to or in combination with the aromatic C5 to C20 radicals in R 4 and their preferred designs.

[0055] Particularly preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein R 4 is a C1- to C2o-alkyl radical, preferably a C1- to C8-alkyl radical, more preferably a C2- to C8-alkyl radical, particularly preferably a C3- to C14-alkyl radical, very particularly preferably a C4- to C8-alkyl radical, most preferably a C5- to C8-alkyl radical. This also preferably applies alternatively to or in combination with the aromatic C5- to C2o-radicals in R 4and their preferred designs.

[0056] Very particular preference is given to a compound according to the invention wherein R 4 heptyl, octyl, nonyl, benzyl or phenyl.

[0057] In the compound according to the invention, the radical R 1 selected from the group consisting of

[0058] - xi) aromatic residues, and

[0059] - xii) aliphatic C3 to Cw residues.

[0060] In some cases, a compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aromatic radicals in xi) comprise a substituent selected from the group consisting of alkyl radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals; particularly preferably alkyl radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals. In other cases, and particularly preferably, the aromatic radicals in xi) do not carry any of the above-mentioned substituents and are preferably not substituted at all. The substituent is preferably in the meta or para position.

[0061] Particularly preferably, the substituent is not in the ortho position. This is particularly advantageous for the longevity of the anti-aging agent.

[0062] Preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein the aromatic radicals in xi) comprise 5 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 8 to 10 carbon atoms, most preferably 6 to 8 carbon atoms.

[0063] Particularly preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein the aromatic radicals in xi) comprise phenyl radicals (ie -CeHs), alpha-methylbenzyl (ie - CH2(CH3)-C6Hs), and / or benzyl radicals (ie -CH2-C6H5), particularly preferably phenyl radicals.

[0064] A compound according to the invention is preferred, preferably as described above and / or below as preferred, wherein the aliphatic C3 to C12 radicals in xii) comprise linear partial radicals, branched partial radicals and / or cyclic partial radicals; are preferably linear, branched or cyclic, most preferably branched.

[0065] Preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein the aliphatic C3 to C12 radicals in xii) are saturated or unsaturated, preferably saturated.

[0066] Particularly preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein in xii) the aliphatic radicals are aliphatic C3 to Cw radicals, preferably aliphatic C4 to Cs radicals, more preferably aliphatic Cs to Cy radicals.

[0067] Preferred is a compound according to the invention, preferably as described above and / or below as preferred, wherein R 1 comprises a tertiary carbon atom with which it is bonded to the nitrogen atom (N). The nitrogen atom (N) is preferably a secondary nitrogen atom.

[0068] In the context of the present invention, the term "tertiary carbon atom" refers to a carbon atom that has only one attached hydrogen atom. This results in a particularly good protective effect compared to secondary and quaternary carbon atoms, preferably in rubber compounds (particularly preferred for vehicle tires and / or other rubber articles that are not vehicle tires (especially technical rubber articles)). In particular, optimized reactivity is achieved in connection with the mechanisms relevant for aging protection, while undesirable side reactions are avoided.

[0069] Particularly preferred is a compound according to the invention wherein R 1 is a branched or cyclic alkyl radical, preferably comprising 3 to 12 carbon atoms, preferably comprising 3 to 8 carbon atoms, particularly preferably comprising 4 to 7 carbon atoms. These are particularly preferably saturated. Cyclic alkyl radicals preferably comprise at least 5 carbon atoms, preferably at least 6. This minimum number is preferably combined with the aforementioned upper limits of carbon atoms.

[0070] Very particular preference is given to a compound according to the invention, preferably as described above and / or below as preferred, wherein R 11,3-dimethylbutyl, phenyl, benzyl, or cyclohexyl, preferably 1,3-dimethylbutyl. This provides a particularly good protective effect in rubber compounds, particularly preferably for vehicle tires and rubber articles other than vehicle tires (preferably technical rubber articles).

[0071] A compound according to the invention is particularly preferred which has the structure according to formula (III):

[0072] (HI).

[0073] The compound of formula (III) has sufficient solubility in polymers, preferably in rubber mixtures, particularly preferably in rubber mixtures for vehicle tires and rubber articles other than vehicle tires (preferably technical rubber articles). Furthermore, the compound of formula (III) can be prepared comparatively easily and in an energy- and cost-saving manner and, compared to 6PPD, exhibits a sufficiently good protective effect (see examples below). The compound of formula (III) according to the invention is also known by IPUAC as

[0074] 2-(1,3-Dimethylbutylamino)-10-octyl-5 / - / -phenophosphazinine 10-oxide.

[0075] Rubber mixture comprising a compound according to formula (I):

[0076] The present invention further relates to a rubber mixture comprising the compound according to the invention as described above (preferably as described above and / or below as preferred, particularly preferably comprising a compound according to formula (III)), preferably comprising one or more than one diene rubber. The rubber mixture comprises one or more than one compound according to the invention, wherein preferably at least one rubber is a diene rubber.

[0077] What has been said above regarding the compound according to the invention, in particular as described above as preferred, preferably also applies mutatis mutandis to the rubber mixture according to the invention.

[0078] The rubber mixture according to the invention thus contains at least one rubber. The rubber mixture according to the invention is, in principle, any rubber mixture in which the compounds according to the invention act as anti-aging agents and / or antiozonants with lower toxicity. The rubber mixture according to the invention comprises one or more rubbers.

[0079] Preferably, a rubber mixture according to the invention, preferably as described above and / or below as preferred, comprises one or more than one compound according to the invention (preferably as described above as preferred), these being the only phenophosphazinine oxides in the rubber mixture.

[0080] A rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising a total amount of the compound according to the invention of 0.1 to 10 phr, preferably of 0.3 to 8 phr, more preferably of 0.6 to 6 phr, particularly preferably of 0.8 to 4.5 phr, most preferably of 1 to 3 phr.

[0081] The term phr (parts per hundred parts of rubber by weight) used in the context of the present invention is the standard quantity used in the rubber industry for compound formulations. The dosage of parts by weight is based on 100 parts by weight of the total mass of all high-molecular-weight (Mw greater than 20,000 g / mol) rubbers present in the mixture.

[0082] The rubber mixture according to the invention, preferably as described above and / or below as preferred, preferably comprises one or more diene rubbers. Diene rubbers are typically referred to as rubbers that are formed by polymerization or copolymerization of dienes and / or cycloalkenes and thus contain C=C double bonds either in the main chain or in the side groups.

[0083] A rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, wherein the diene rubber is 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, liquid rubbers with a molecular weight Mw of greater than 20,000 g / mol, butyl rubber (HR), halobutyl rubber (XIIR), 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.

[0084] In the context of the present invention, the terms “natural rubber” and “natural rubber”, both terms having an identical scope of meaning, are understood to mean naturally occurring rubber obtained from Hevea rubber trees and / or “non-Hevea” sources.

[0085] Preferred non-Hevea sources are guayule shrubs and dandelions. A particularly preferred dandelion is TKS (Taraxacum kok-saghyz; Russian dandelion).

[0086] Particularly preferred is a rubber mixture according to the invention, preferably as described above and / or below as preferred, wherein the diene rubber is selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR), emulsion-polymerized styrene-butadiene rubber (ESBR), butyl rubber (IIR) and halobutyl rubber (XHR).

[0087] Very particular preference is given to a rubber mixture according to the invention, preferably as described above and / or below as preferred, wherein the 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] Nitrile rubber, hydrogenated acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber (HR), halobutyl rubber (XHR), and / or ethylene propylene diene rubber are preferably used in the production of rubber articles that are not vehicle tires (but are otherwise typically considered technical rubber articles), preferably for belts, straps, hoses, tapes, and / or shoe soles. The blend compositions known to those skilled in the art for these rubbers—specific with regard to fillers, plasticizers, vulcanization systems, and additives—are preferred.

[0089] Polyisoprene preferably comprises c / s-1,4-polyisoprene and / or 3,4-polyisoprene. This preferably applies regardless of whether the polyisoprene is natural or synthetic. Preference is given to c / s-1,4-polyisoprene, particularly preferably with a c / s-1,4 fraction greater than 90% by weight. Such a polyisoprene is preferably obtained by stereospecific polymerization in solution with Ziegler-Natta catalysts or using finely divided lithium alkylene. Furthermore, natural rubber (NR) is also such a c / s-1,4 polyisoprene. Particular preference is therefore given to natural rubber (NR) comprising c / s-1,4-polyisoprene, preferably with a c / s-1,4 fraction greater than or equal to 99% by weight.

[0090] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising one or more natural polyisoprene (NR) and one or more synthetic polyisoprene (IR). Thus, a mixture of polyisoprene is preferably present.

[0091] In some cases, a rubber mixture according to the invention is particularly preferred, preferably as described above and / or below as preferred, comprising one or more than one natural polyisoprene (NR), preferably in a total amount of 56 to 130 phr, particularly preferably 80 to 120 phr, very particularly preferably 90 to 110 phr, further preferably 95 to 100 phr. Such a rubber mixture exhibits, in particular, optimized tear properties and abrasion properties while simultaneously having good processability and reversion stability. A further preferred total amount is in the range of 56 to 100 phr, preferably 80 to 100 phr, further preferably 90 to 100 phr.

[0092] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising one or more than one natural polyisoprene (NR), the total amount of which is significantly less than 100 phr. In these cases, the rubber mixture additionally comprises one or more than one rubber different from natural polyisoprene, preferably another diene rubber, particularly preferably selected from the group consisting of synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR), and emulsion-polymerized styrene-butadiene rubber (ESBR). Particularly preferred in these cases is a rubber mixture according to the invention comprising one or more than one natural polyisoprene (NR) in a total amount of 5 to 55 phr, preferably 5 to 35 phr, more preferably 5 to 25 phr, most preferably 5 to 20 phr.Such a rubber compound shows in particular good processability and reversion stability as well as optimized tear properties and optimal rolling resistance behavior.

[0093] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising at least one butadiene rubber (BR, polybutadiene). Preference is given to a butadiene rubber comprising a high-c / s and / or a low-c / s type, with polybutadiene with a c / s fraction greater than or equal to 90 wt. % being referred to as a high-c / s type and polybutadiene with a c / s fraction less than 90 wt. % being referred to as a low-c / s type. A particularly preferred low-c / s type comprises Li-BR (lithium-catalyzed butadiene rubber), preferably with a c / s fraction of 20 to 50 wt. %. A high-c / s type is particularly preferred, since this achieves particularly good properties, in particular low hysteresis of the rubber mixture.

[0094] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, wherein the butadiene rubber is end-functionalized by means of one or more functional groups and / or functionalized along the polymer chains. Preferably, the one or more functional groups are independently selected from the group consisting of hydroxy groups, ethoxy groups, epoxy groups, siloxane groups, amino groups, aminosiloxane groups, carboxy groups, phthalocyanine groups, and silane sulfide groups. However, the selection of the functional group is preferably not limited to the above groups. In some cases, the functional group preferably comprises one or more metals.

[0095] A rubber mixture according to the invention, preferably as described above and / or below as preferred, is preferred, comprising the one or more butadiene rubbers in a total amount of 10 to 80 phr, preferably 12 to 50 phr, particularly preferably 15 to 40 phr. This achieves particularly good tear and abrasion properties of the rubber mixture according to the invention and optimal braking behavior.

[0096] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising at least one styrene-butadiene rubber (styrene-butadiene copolymer). Preference is given to a styrene-butadiene rubber comprising one or more than one solution-polymerized styrene-butadiene rubber (SSBR) and / or one or more than one emulsion-polymerized styrene-butadiene rubber (ESBR). In the context of the present invention, the terms "styrene-butadiene rubber" and "styrene-butadiene copolymer" are used synonymously. In some cases, a rubber mixture according to the invention is preferred in which the styrene-butadiene rubber is end-group-functionalized by means of one or more than one functional group and / or is functionalized along the polymer chains. Regarding preferred functional groups, what was said above regarding butadiene rubber applies accordingly.

[0097] A rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising the at least one styrene-butadiene rubber (SSBR) in a total amount of 10 to 80 phr, preferably 30 to 75 phr, particularly preferably 50 to 70 phr. A rubber mixture according to the invention is particularly preferred which comprises one or more than one solution-polymerized styrene-butadiene rubber (SSBR), which is additionally present in a total amount of 10 to 80 phr, preferably 30 to 75 phr, particularly preferably 50 to 70 phr. This achieves particularly good rolling resistance properties of the rubber mixture according to the invention. The solution-polymerized styrene-butadiene rubber (SSBR) is particularly preferably used in combination with one or more than one further rubber. This typically results in an improved and more balanced property profile.

[0098] In addition to one or more than one compound according to the invention and at least one rubber, the rubber mixture according to the invention preferably additionally comprises ingredients, preferably at least one filler.

[0099] A rubber mixture according to the invention, preferably as described above and / or below as preferred, additionally comprises one or more than one filler, preferably in a total amount of 30 to 500 phr, preferably 50 to 400 phr, more preferably 80 to 300 phr. A particularly preferred filler is a reinforcing filler, particularly preferably selected from the group consisting of carbon blacks and silicon dioxides.

[0100] In principle, all types of carbon black known to those skilled in the art are suitable as carbon black. The carbon black is preferably selected from the group consisting of industrial carbon black and pyrolysis carbon black, with industrial carbon black being preferred.

[0101] The carbon black preferably has an iodine number, according to ASTM D 1510 (also referred to as iodine adsorption number), in a range from 30 to 250 g / kg, preferably from 35 to 215 g / kg, more preferably from 40 to 180 g / kg, and most preferably from 45 to 140 g / kg, and / or a DBP number, according to ASTM D 2414, in a range from 30 to 200 ml / 100 g, preferably from 70 to 170 ml / 100 g, more preferably from 90 to 140 ml / 100 g. The DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light-colored filler using dibutyl phthalate. The use of such a carbon black in the rubber mixture according to the invention, especially for vehicle tires, typically ensures the best possible compromise between abrasion resistance and heat buildup, which in turn influences the ecologically relevant rolling resistance. A carbon black with an iodine number in the range of 80 to 110 g / kg and a DBP number in the range of 100 to 130 ml / 100 g is particularly preferred.A carbon black of type N339 is particularly preferred.

[0102] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, wherein the carbon black is present in the rubber mixture in a total amount in the range from 0.1 to 60 phr, preferably from 3 to 40 phr, more preferably from 4 to 30 phr, most preferably from 5 to 15 phr. In these amounts, the carbon black is typically present as a supplementary filler in combination with a main filler, preferably one or more silicon dioxides, more preferably silicic acid.

[0103] In other cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, wherein the carbon black is present in the rubber mixture in a total amount in the range from 30 to 300 phr, preferably from 35 to 200 phr, particularly preferably from 40 to 100 phr. In these amounts, carbon black is present in particular as the sole or as the main filler (more than 50 wt.% based on the total filler amount; preferably in combination with comparatively small amounts of silica).

[0104] Preferably, the silicon dioxide is amorphous silicon dioxide and / or fumed silicon dioxide. A particularly preferred amorphous silicon dioxide comprises precipitated silica, also referred to as precipitated silicon dioxide. In the context of the present invention, the terms "silica" and "silica" are synonymous and therefore synonymous.

[0105] Particularly preferred is amorphous silicon dioxide, preferably precipitated silica, with a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) in the range of 35 to 400 m 2 / g, preferably from 50 to 350 m 2 / g, particularly preferably from 85 to 320 m 2 / g, most preferably from 120 to 235 m 2 / g, and / or (preferably and) with a CTAB surface area (according to ASTM D 3765) in the range of 30 to 400 m 2 / g, preferably from 50 to 330 m 2 / g, particularly preferably from 80 to 300 m 2 / g, most preferably from 115 to 200 m 2 / g. Such silicon dioxide, for example, leads to particularly good physical properties of the vulcanizates in rubber compounds for tire treads. Furthermore, it can offer advantages in compound processing by reducing mixing times while maintaining consistent product properties, leading to improved productivity. Particular preference is given to a type U silica, such as Itrasil® VN3 (trade name) from Evonik, as well as highly dispersible silicas (so-called HD silicas). Preferred highly dispersible silicas include Zeosil® 1165 MP from Solvay.

[0106] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising at least one silica, preferably in a total amount in the range from 30 to 500 phr, more preferably from 50 to 400 phr, particularly preferably from 80 to 300 phr. In these amounts, silica is present in particular as the sole or as the main filler (more than 50 wt.% based on the total filler amount; preferably in combination with comparatively small amounts of carbon black).

[0107] In some cases, a rubber mixture according to the invention is particularly preferred, preferably as described above and / or below as preferred, comprising at least one silica, preferably in a total amount in the range from 5 to 100 phr, more preferably from 7 to 80 phr, particularly preferably from 10 to 60 phr. In these amounts, silica is typically present as a supplementary filler in combination with a main filler, preferably a carbon black.

[0108] Particularly preferred is a rubber mixture according to the invention, preferably as described above and / or below as preferred, comprising at least one silica and at least one carbon black, wherein the total amount of silica is in the range from 50 to 300 phr, preferably from 80 to 200 phr, and the total amount of carbon black is in the range from 5 to 60 phr, preferably from 7 to 40 phr.

[0109] The rubber mixture according to the invention preferably comprises, preferably as described above and / or below as preferred, additional fillers, ie, which are not or do not comprise carbon black, silicon dioxide, or silica. These additional fillers preferably also comprise reinforcing fillers and / or non-reinforcing fillers.

[0110] Preferred non-reinforcing fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide, rubber gels, and / or fibers. Preferred fibers include aramid fibers, glass fibers, carbon fibers, and / or cellulose fibers.

[0111] Preferred reinforcing fillers include carbon nanotubes, graphite, graphene, and / or so-called "carbon-silica dual-phase fillers." The carbon nanotubes preferably comprise unmodified carbon nanotubes and / or carbon nanotubes modified with functional groups, with preferred functional groups being selected from the group consisting of hydroxyl, carboxyl, and carbonyl groups.

[0112] In the context of the present invention, zinc oxide is not one of the fillers within the meaning of the present invention.

[0113] A rubber mixture according to the invention, preferably as described above and / or below as preferred, preferably comprises one or more further additives. These are typically conventional additives in the typical amounts that are preferably added in at least one basic mixing stage during the production of the rubber mixture.

[0114] Preferably, the one or more than one further additive comprises: a) anti-aging agents which are known from the prior art and which are not a compound of the formula (I) according to the invention, or other compounds according to the invention; preferably comprising para-phenylenediamines and / or dihydroquinolines; particularly preferably selected from the group consisting of 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), and

[0115] 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ); b) an activator; preferably comprising zinc compounds (including zinc complexes) and / or fatty acids; particularly preferably comprising zinc oxide, stearic acid and / or zinc ethylhexanoate; c) agents for the binding of fillers (in particular for carbon black and silica); preferably comprising S-(3-aminopropyl)-thiosulfuric acid, its metal salts (in particular for the binding to carbon black) and / or silane coupling agents (in particular for the binding to silicon dioxide, in particular to silica); d) antiozonant waxes; e) resins; preferably tackifier resins; f) mastication aids; preferably comprising 2,2'-dibenzamidodiphenyl disulfide (DBD); g) processing aids; preferably comprising fatty acid esters and / or metal soaps, preferred metal soaps comprising zinc soaps and / or calcium soaps; and / or h) plasticizers;preferably comprising oils (preferably comprising aromatic, naphthenic and / or paraffinic mineral oils), resins and / or liquid polymers;particularly preferably comprising MES (mild extraction solvate), DAE (distilled aromatic extracts), RAE (residual aromatic extract), TDAE (treated distillate aromatic extract), rubber-to-liquid oils (RTL), biomass-to-liquid oils (BTL) (preferably with a polycyclic aromatics content of less than 3 wt.% according to method IP 346), triglycerides (preferably rapeseed oil), a factice, hydrocarbon resins, and / or liquid polymers with an average molecular weight (determined by GPC = gel permeation chromatography, based on BS ISO 11344:2004) between 500 and 20,000 g / mol. When using mineral oil, it is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts), RAE (Residual Aromatic Extract), TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvents) and naphthenic oils.;

[0116] Particularly preferred in most cases is a rubber mixture according to the invention, preferably as described above and / or below as preferred, which is substantially free from, preferably not comprising, 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), and optionally additionally from 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ); more preferably is substantially free from, preferably not comprising, para-phenylenediamines and optionally additionally from dihydroquinolines; most preferably substantially free from, preferably not comprising, anti-aging agents which are not a compound of the invention (ie anti-aging agents known and customary in the art).It is therefore particularly preferred that the rubber mixture according to the invention contains, as the sole age-inhibitor, one or more than one compound according to the invention, preferably as described above as being preferred. In the context of the present invention, “essentially free from” means an upper amount of 0.1 phr, preferably a total amount in the range from 0 phr to 0.1 phr, particularly preferably from 0.0001 phr to 0.1 phr. The amount is particularly preferably zero (0), ie, “not comprising”. With these very preferably small amounts, including zero (0) phr, it is possible to achieve a comparable protective effect with significantly lower toxicity. Here, the compound according to the invention replaces the aforementioned para-phenylenediamines known from the prior art and typically used.In some other cases, a rubber mixture according to the invention is preferred in which at least some of the anti-aging agents that are not compounds according to the invention (especially para-phenylenediamines) are replaced by one or more compounds according to the invention, preferably 50% by weight or more. This at least partially achieves the advantage according to the invention, although not yet to the optimal extent.

[0117] As defined above, the additional absence of dihydroquinolines, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), is optional, i.e. desirable in some cases, undesirable in others. In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising (irrespective of whether para-phenylenediamines are present or not) one or more than one dihydroquinoline, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ). Preferably, the dihydroquinoline, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), is comprised in a total amount in the range from 0.1 to 3 phr in the rubber mixture according to the invention, preferably from 0.5 to 1.5 phr.

[0118] Ozone protection waxes (see d) above) are considered separately and are preferably contained in the rubber mixture according to the invention, regardless of whether ageing inhibitors according to a) are contained or not.

[0119] The silane coupling agents (see c) above) are preferably all types known to the person skilled in the art. The rubber mixture according to the invention preferably comprises one or more silane coupling agents, preferably as described above and / or below as preferred. In some cases, the rubber mixture according to the invention preferably comprises a mixture of different silanes.

[0120] Silane coupling agents react with the surface silanol groups of the silicon dioxide (especially silica) or other polar groups, either during the mixing of the rubber or rubber compound in situ or before its addition to the rubber during a pretreatment (premodification).

[0121] Preferred silane coupling agents include bifunctional organosilanes that have at least one alkoxy, cycloalkoxy, or phenoxy group as a leaving group on the silicon atom and, as an additional functionality, a group that can (optionally after cleavage) enter into a chemical reaction with the double bonds of the polymer. Preferred groups include -SCN, -SH, -NH2, and / or -Sx- (where x = 2 to 8). Silanes with an -SH group are typically also referred to as mercaptosilanes. Preferred mercaptosilanes include blocked mercaptosilanes, preferably according to WO 99 / 09036 A1.

[0122] Particularly preferred silane coupling agents include 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane, 3,3'-bis(triethoxysilylpropyl)polysulfides having 2 to 8 sulfur atoms (particularly preferably 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT) and / or its disulfide (TESPD)), and / or mixtures of the sulfides, each preferably with a different number of sulfur atoms. In some cases, TESPT is preferred, particularly preferably as a mixture with carbon black (trade name X50S® from Evonik).

[0123] Preferred silane coupling agents additionally or alternatively include those according to WO 2008 / 083241 A1, WO 2008 / 083242 A1, WO 2008 / 083243 A1 and / or WO 2008 / 083244 A1. Further preferred silane coupling agents, additionally or alternatively, include silanes marketed under the name NXT in various variants by Momentive, USA (preferably 3-octanoylthio-1-propyltriethoxysilane) and / or silanes marketed under the name VP Si 363® by Evonik Industries.

[0124] Preferred is a rubber mixture according to the invention, preferably as described above and / or below as preferred, wherein the one or more than one further additive is comprised in a total amount in the range from 3 to 150 phr, preferably from 4 to 100 phr, more preferably from 5 to 80 phr.

[0125] A rubber mixture according to the invention is preferred, preferably as described above and / or below as preferred, comprising one or more than one activator (see b) above); preferably a zinc compound, particularly preferably zinc oxide. There is preferably no restriction on the types of zinc oxide. Preference is given to granules and / or powders. The zinc oxide preferably has a BET surface area of ​​up to 100 m 2 / g, preferably in a range of 1 to 100 m 2 / g. In some cases, a zinc oxide is preferred, where the BET surface area is less than 10 m 2 / g. In other cases, a zinc oxide is preferred, with a BET surface area in the range of 10 to 100 m 2 / g, particularly preferred are so-called “nano-zinc oxides”.

[0126] A rubber mixture according to the invention, preferably as described above and / or below as preferred, is preferably vulcanized or partially vulcanized, preferably vulcanized. This means that it is preferably used in vulcanized or at least partially vulcanized form, particularly preferably in a vehicle tire or in rubber articles that are not vehicle tires (preferably technical rubber articles). In the context of the present invention, the terms "vulcanized" and "crosslinked" are used synonymously. Therefore, the rubber mixture according to the invention is preferably a crosslinked rubber mixture. However, it is of course clear to the person skilled in the art that the rubber mixture is typically unvulcanized until the relevant processing.

[0127] The vulcanization or vulcanization of the rubber mixture according to the invention is preferably carried out in the presence of sulfur and / or sulfur donors, preferably with the assistance of vulcanization accelerators, wherein preferably some vulcanization accelerators are also sulfur donors.

[0128] A rubber mixture according to the invention, preferably as described above and / or below as preferred, preferably comprises sulfur and / or one or more than one sulfur donor. There are no particular restrictions with regard to the sulfur donors, so that in principle all sulfur donors known to the person skilled in the art are suitable, as long as they provide sulfur in an appropriate form under the prevailing conditions.

[0129] Preferably, a rubber mixture according to the invention comprises (alternatively or in addition to a sulfur donor) one or more than one vulcanization accelerator.

[0130] Preferred vulcanization accelerators include thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate accelerators, and / or guanidine accelerators. Particularly preferred is one or more sulfenamide accelerators and / or one or more guanidine accelerators, most particularly one or more accelerators selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazyl-2-sulfenemorpholide (MBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and diphenylguanidine (DPG).

[0131] A rubber mixture according to the invention, preferably as described above and / or below as preferred, preferably comprises one or more than one vulcanization retarder. The presence of a vulcanization retarder contributes, for example, to a better-balanced vulcanization process.

[0132] The rubber mixture according to the invention is preferably produced or provided, particularly preferably produced. This is preferably carried out by processes customary in the rubber industry, in which firstly in one or more mixing stages a base mixture is provided with all components except (i.e. minus) the vulcanization system, wherein the vulcanization system comprises the sulfur and the vulcanization-influencing compounds, i.e. preferably the total amount of sulfur, sulfur donor, vulcanization accelerator and vulcanization retarder. By adding the vulcanization system in a final mixing stage, a finished mixture is produced which is preferably further processed by extrusion and / or calendering and brought into the desired shape. The shape achieved in this way preferably determines the subsequent use, for example in a vehicle tire.

[0133] A rubber mixture according to the invention is preferably used in a vulcanizate.

[0134] Further preferred is a rubber mixture according to the invention for use in a vehicle tire, preferably in an outer or inner component of a vehicle tire, preferably an outer component.

[0135] A rubber mixture according to the invention, preferably as described above and / or below as preferred, is preferred, comprising one or more than one strength member, preferably comprising fibers, fabrics and / or cords.

[0136] Vehicle tires comprising the rubber mixture according to the invention:

[0137] The present invention also relates to a vehicle tire, preferably a pneumatic vehicle tire, comprising the rubber mixture according to the invention as described above, preferably as described above as preferred, in at least one component, preferably in at least one outer component, wherein the outer component is preferably a tread, a sidewall, and / or a flange profile. The above statements regarding the compound according to the invention and the rubber mixture according to the invention, each including preferred embodiments, preferably also apply mutatis mutandis to the vehicle tire according to the invention.

[0138] The vehicle tire according to the invention is preferably vulcanized, i.e., not a green vehicle tire. The vulcanized vehicle tire preferably comprises, in at least one component, a vulcanizate of at least one rubber mixture according to the invention. It is known to those skilled in the art that most compounds, such as the rubbers contained therein, are, or can be, in a chemically altered form either immediately after mixing or only after vulcanization.

[0139] The vehicle tire according to the invention, preferably as described above and / or below as preferred, preferably comprises a pneumatic vehicle tire and / or a solid rubber tire.

[0140] Preferably, the vehicle tire according to the invention, preferably as described above and / or below as preferred, is selected from the group consisting of industrial and construction vehicle tires, truck, passenger car and two-wheel tires.

[0141] Particularly preferred is a vehicle tire according to the invention, preferably as described above and / or below as preferred, which has the rubber mixture according to the invention in two, three or more than three components.

[0142] Use of the compound according to the invention and the rubber mixture according to the invention:

[0143] The present invention relates very generally to a use of the compound according to the invention, preferably as described above as preferred, as an age-protecting agent and / or (preferably and) antioxidant in a rubber mixture, preferably in a rubber mixture according to the invention (preferably as described above as preferred). The present invention also relates to a use of the compound according to the invention, preferably as described above and / or below as preferred, as an age-protecting agent and / or antioxidant (preferably as an age-protecting agent), preferably in

[0144] - vehicle tyres, particularly pneumatic vehicle tyres;

[0145] - rubber articles other than vehicle tires, particularly preferably selected from the group consisting of air springs, bellows, bands, belts, straps, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robot applications, shoe soles and parts of a shoe sole;

[0146] - oils and / or fats; and / or

[0147] - Fuels and / or lubricants.

[0148] The above statements regarding the compound according to the invention (including preferred embodiments) and the rubber mixture according to the invention (including preferred embodiments) preferably also apply mutatis mutandis to the use according to the invention as an age-protecting agent and / or antioxidant.

[0149] Preferred belts include conveyor belts.

[0150] In some cases, the use of the compound according to the invention as an age-protecting agent and / or antioxidant in oils, fats, fuels and / or lubricants is preferred, particularly preferably in connection with use for engines.

[0151] The present invention also relates to a use of the rubber mixture according to the invention, preferably as described above and / or below as preferred, for producing a

[0152] - vehicle tyre, preferably a pneumatic vehicle tyre; and / or

[0153] - rubber article which is not a vehicle tire, particularly preferably selected from the group consisting of air springs, bellows, bands, belts, straps, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robot applications, shoe soles and parts of a shoe sole.

[0154] The above statements regarding the compound according to the invention (including preferred embodiments) and the rubber mixture according to the invention (including preferred embodiments) preferably also apply mutatis mutandis to the inventive use for production as described above. The statements below preferably also apply mutatis mutandis to the vehicle tire according to the invention.

[0155] Preference is given to using the compound for producing all tire components (including outer and / or inner components), preferably for producing an outer component, particularly preferably for producing a flange profile, tread, and / or sidewall. Particular preference is given to using the compound for producing a cap of a tread having a cap / base construction. Different shaping during extrusion or calendering preferably determines the type of component. Preferred inner components include a squeegee, an inner layer, an apex profile, a belt, a shoulder, a belt profile, a carcass, a bead reinforcer, a bead profile, and / or a bandage. Rubber compounds for inner components are typically also referred to as body compounds. The various components, with their respective shapes and in the unvulcanized state, typically serve to construct a green tire.The unvulcanized green tire is then preferably vulcanized.

[0156] The use according to the invention also relates to the production of rubber articles other than vehicle tires. These rubber articles preferably have a structure consisting of several layers; particularly preferably, one or more layers comprise at least one reinforcement member.

[0157] Preferred belts include rubber belts and / or conveyor belts.

[0158] Preferably, the compound according to the invention, preferably as described above as preferred, is not used as a dye, pigment, in pharmaceutical products, or in electronic devices (particularly preferably in displays, especially OLED displays). Process for preparing the compound according to the invention:

[0159] The present invention also relates to a process for preparing a compound according to the invention, preferably a compound according to formula (I), comprising the process steps: i) preparing or providing a compound according to formula (B1):

[0160] (B1 ), ii) reacting the compound according to formula (B1 ) with

[0161] - hydrogen and a ketone or aldehyde, preferably a ketone, to give the compound of formula (I):

[0162] (I), where

[0163] - R 1 is selected from the group consisting of

[0164] - xi) aromatic residues, and

[0165] - xii) aliphatic C3 to C12 residues,

[0166] - R 2 and R 3are the same or different and are independently selected from the group consisting of aliphatic Ci to Ci2 residues, aromatic residues, halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether residues, - R 4 is selected from the group consisting of aliphatic Ci to C2o residues and aromatic Cs to C2o residues,

[0167] - X represents oxygen or sulfur, preferably oxygen,

[0168] - m is 0 or 1 or 2 or 3,

[0169] - n is 0 or 1 or 2 or 3 or 4, and

[0170] - Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, amino and nitro, preferably amino and nitro.

[0171] What has been said above regarding the compound according to the invention (preferably and in particular regarding compounds according to the invention which are defined above as preferred) preferably also applies mutatis mutandis to the process for preparing the invention. This means that for R 1 , R 2 , R 3 , R 4 , m and n all the above statements made in connection with the description of the compound according to the invention apply, including preferred embodiments and with regard to the possibilities of any gradation in the preference and combination of these features.

[0172] Preferably, the halogens in Z comprise chlorine, bromine, or iodine, preferably chlorine. It particularly preferably does not comprise fluorine.

[0173] Preferably, in Z, the sulfonate-based leaving groups comprise triflate, nonaflate, mesylate or tosylate.

[0174] Z is very preferably nitro or amine, particularly preferably nitro. This means that very preferred starting compounds are corresponding amino or nitro reactants.

[0175] Preference is given to a process according to the invention, preferably as described above and / or below as preferred, wherein the reaction in step ii) with hydrogen is carried out using a catalyst, preferably using a hydrogenation catalyst. This means that such a catalyst is preferably used or employed in step ii). In some cases, a "hydrogenation catalyst" is also referred to as a "hydrogenation catalyst," wherein in the context of the present invention, both terms have the same scope of meaning.

[0176] Preference is given to a process according to the invention, preferably as described above and / or below as preferred, wherein in step ii) the catalyst, preferably the hydrogenation catalyst, comprises a metal, preferably one or more than one metal selected from the group consisting of nickel, copper, iron, chromium, aluminum, palladium, and platinum. Particularly preferably, the catalyst, preferably the hydrogenation catalyst, comprises a noble metal, particularly preferably palladium (Pd) and / or platinum (Pt). In other words, a noble metal catalyst is particularly preferred.

[0177] The metal, preferably the noble metal, is preferably used on carbon (C). Particularly preferred catalysts include palladium on carbon (Pd / C), platinum on carbon (Pt / C), Raney nickel, and / or copper chromite; palladium on carbon (Pd / C) and / or platinum on carbon (Pt / C) are particularly preferred.

[0178] Preference is given to a process according to the invention, preferably as described above and / or below as preferred, wherein the reaction in step ii) with hydrogen is carried out for a period of 1 to 30 hours, preferably 3 to 22 hours, particularly preferably 5 to 16 hours, especially preferably 8 to 13 hours.

[0179] Preference is given to a process according to the invention, preferably as described above and / or below as preferred, wherein the reaction with hydrogen in step ii) takes place in a pressure reactor, preferably in an autoclave.

[0180] Particularly preferred is a process according to the invention, wherein the reaction in step ii)

[0181] - by means of a catalyst; and / or (preferably and)

[0182] - at a temperature of 40 to 190°C, preferably from 55 to 170°C, particularly preferably from 70 to 150°C, especially preferably from 85 to 130°C; and / or (preferably and)

[0183] - at a pressure of 20 to 70 bar, preferably 28 to 57 bar, particularly preferably 35 to 45 bar. In the process according to the invention, the ketone in step ii) is the ketone derivative of the subsequent radical R 1 ; in the case of an aldehyde, it is the aldehyde derivative. A ketone is particularly preferred, most preferably methyl isobutyl ketone (MIBK).

[0184] Preference is given to a process according to the invention, preferably as described above and / or below as preferred, wherein in step ii) a solvent is used, wherein preferably the solvent is identical to the ketone or aldehyde or is different from the ketone or aldehyde (preferably identical).

[0185] If the ketone or aldehyde is identical to the solvent, the solvent is also a reaction partner. This is preferably the case if the aldehyde or ketone is in liquid form under reaction conditions. If the ketone or aldehyde is not in liquid form under reaction conditions, the solvent is preferably inert, i.e. it is not itself a reaction partner. Preferred inert solvents include toluene, a dioxane (preferably 1,4-dioxane), 2-methyltetrahydrofuran (2-MTHF) and / or xylene. This is preferably the case if the aldehyde or ketone is in solid form under reaction conditions. In the latter case, the ketone or aldehyde is preferably used as a reactant only in the stoichiometrically required amounts (in some cases preferably in a slight excess).

[0186] Particularly preferred is a process according to the invention, preferably as described above and / or below as preferred, wherein the ketone or aldehyde, particularly preferably the ketone, is present in liquid form in step ii), particularly preferably as solvent and reactant. This eliminates the need for an additional compound such as toluene or xylene.

[0187] A process according to the invention is preferred, preferably as described above and / or below as preferred, wherein after step ii) one or more purification steps are carried out, preferably filtration, chromatography, recrystallization, and / or washing with a solvent. A preferred solvent, which is preferably different from the solvent used in step ii), comprises an alcohol and / or 2-MTHF, preferably methanol and / or ethanol, particularly preferably ethanol. Chromatography comprising silica gel is preferred.

[0188] Recrystallization from hydrocarbons, preferably from C5 to C20 aliphatic compounds, particularly preferably from cyclohexane and / or cycloheptane, is preferred.

[0189] The invention is explained in more detail below using exemplary embodiments.

[0190] Synthesis of a compound according to formula (I):

[0191] The compound according to formula (III), as an exemplary embodiment of a compound according to formula (I), was prepared in several steps in the following concrete manner:

[0192] 1st step (synthesis of 5 / 7-phenophosphazinine 10-oxide):

[0193] 5H-phenophosphazinine 10-oxide was prepared according to M. Haering, Helvetica Chimica Acta, 1960, 43, 1826-1840, and additionally recrystallized from methanol. A compound of formula (a) was obtained:

[0194] 2nd step (10-octyl-5 / - / -phenophosphazinine 10-oxide):

[0195] The 5H-phenophosphazinine 10-oxide obtained in the first step was converted in the second step under protective gas to 10-octyl-5H-phenophosphazinine 10-oxide. 1.50 g (6.97 mmol, 1 eq) of 5H-phenophosphazinine 10-oxide was dissolved in 30 mL of DMA (dimethylacetamide). To this solution were added 114 mg (0.70 mmol, 0.1 eq) of AIBN (azobis(isobutyronitrile)) and 1.54 mL of 1-octene (9.76 mmol, 1.4 eq), heated to 85°C, and stirred overnight. The solvent was then removed under vacuum. The product was a colorless oil with a yield of 2.25 g (99% of theory). A compound of formula (b) was obtained:

[0196] 1 H-NMR (500 MHz, DMSO-c / 6) 5 = 10.07 (s, 1H), 7.75 (ddd, J = 11.9, 7.7, 1.5 Hz, 2H), 7.51 (ddd, J = 8.5, 7.1, 1.5 Hz, 2H), 7.15 (dd, J = 8.3, 5.2 Hz, 2H), 7.08 (td, J = 7.4, 1.3 Hz, 2H), 2.09 - 1.96 (m, 2H), 1.21 - 0.94 (m, 12H), 0.80 (t, J = 7.2 Hz, 3H).

[0197] 13C-NMR (126 MHz, DMSO-c / 6) ö = 142.6, 142.5, 132.9, 130.8, 130.7, 120.7, 120.6, 116.4, 116.3, 112.1, 111.3, 33.2, 31.5, 30.2, 28.8, 25.9, 22.5, 21.4, 14.8.

[0198] 31 P-NMR (202 MHz, DMSO-c / 6) 6 = 13.7.

[0199] Mass spectrometry result: ESI-MS [M+H] + = 328.

[0200] In an alternative synthesis, the compound of formula (b) was prepared according to “Chemistry of phosphorus heterocycles”, M. Tajbakhsh-Jadidi, PhD thesis, Manchester (1980) (synthesis not further elaborated).

[0201] 3rd step (2-nitro-10-octyl-5 / - / -phenophosphazine 10-oxide):

[0202] At room temperature, 0.95 g (2.90 mmol) of 10-octyl-5-phenophosphazine 10-oxide was dissolved in 20 mL of glacial acetic acid. A solution of 2.25 mL of 65% nitric acid and 3.15 mL of glacial acetic acid was added dropwise to this solution, the temperature not exceeding 25°C. An orange solution formed, which was poured onto ice after one hour, so that a solid could then be filtered off. The solid was then dissolved in DCM (alternatively CHCh / n-BuOH 3:1) (a little triethylamine was added if necessary) and extracted with saturated sodium hydrogen solution and brine. The mixture was dried over sodium sulfate, the inorganic components were removed by filtration, and the solvent was removed in vacuo. The resulting solid was purified by crystallization from 2-MeTHF (or alternatively by column chromatography with dichloromethane / methanol; 100:0 -> 95:5). A compound of formula (c) was obtained.The compound was obtained as a lemon yellow solid with a yield of 0.8 g (74% of theory).

[0203] X H-NMR (500 MHz, DMSO-c / 6) 5 = 10.92 (s, 1H), 8.62 (dd, J = 12.3, 2.7 Hz, 1H), 8.33 (dd, J = 9.2, 2.7 Hz, 1H), 7.89 - 7.81 (m, 1H), 7.63 (t, J = 7.7 Hz, 1H), 7.34 - 7.23 (m, 3H), 2.13 (qq, J = 14.7, 6.8, 6.1 Hz, 2H), 1.22 - 0.97 (m, 12H), 0.80 (td, J = 7.3, 3.2 Hz, 3H).

[0204] 13 C-NMR (126 MHz, DMSO-c / 6) 6 = 147.1, 141.1, 140.2, 133.6, 131.0, 128.3, 128.0, 123.0, 117.5, 112.8, 112.1, 111.4, 31.5, 30.0, 29.9, 28.7, 28.6, 22.5, 22.2, 14.3.

[0205] 31 P-NMR (202 MHz, DMSO-c / 6) 6 = 13.91.

[0206] Mass spectrometry result: ESI-MS [M+H] + = 373.

[0207] 4th step (2-(1,3-Dimethylbutylamino)-10-octyl-5 / - / -phenophosphazine-10-oxide):

[0208] In a stainless steel autoclave equipped with a Teflon liner, 163 mg (0.44 mmol) of 2-nitro-10-octyl-5H-phenophosphazinine 10-oxide, 37 mg of platinum on carbon (5%; 0.4 g per 4.67 mmol of substrate), and 20.0 mL of methyl isobutyl ketone (MlbK) were weighed. Subsequently, 40 bar of hydrogen was applied, and the reaction mixture was stirred at 120°C for 10 hours. After the reaction, the excess hydrogen was vented. The reaction product was a suspension, which was filtered through Celite and subsequently washed with ethanol. The resulting filtrate was concentrated to dryness and then further dried under vacuum. The resulting dried product was purified by crystallization from cyclohexane. The purified product was a violet-brown solid; yield 155 mg (83% of theory). The compound according to formula (III) was obtained.

[0209] XH-NMR (500 MHz, DMSO-c / 6) 5 = 9.66 (s, 1H), 7.67 (dd, J = 11.9, 7.7 Hz, 1H), 7.45 - 7.39 (m, 1H), 7.05 (dd, J = 8.4, 5.3 Hz, 1H), 6.96 (q, J = 7.6 Hz, 2H), 6.85 (d, J = 29.3 Hz, 2H), 4.27 (s, 1H), 3.09 (qd, J = 7.3, 4.8 Hz, 1H), 1.93 (ddd, J = 15.1, 9.9, 5.9 Hz, 2H), 1.71 (dddt, J = 19.5, 13.1, 8.2, 6.6 Hz, 2H), 1.45 (dtd, J = 13.7, 7.1, 3.1 Hz, 1H), 1.18 (td, J = 7.2, 2.7 Hz, 2H), 1.09 (dt, J = 10.2, 6.2 Hz, 8H), 0.93 (d, J = 6.6 Hz, 3H), 0.88 (dd, J = 6.6, 4.9 Hz, 2H), 0.87 - 0.83 (m, 6H), 0.80 (td, J = 7.2, 1.1 Hz, 3H).

[0210] 31 P-NMR (202 MHz, DMSO-c / 6) 6 = 14.37.

[0211] Ergebnis Massenspektrometrie: ESI-MS [M+H] + = 427.

[0212] Weitere Verbindungen der Formel (I):

[0213] In an alternative synthesis, starting from “Chemistry of phosphorus heterocycles”, M. Tajbakhsh-Jadidi, PhD thesis, Manchester (1980), a compound of formula (II) was prepared analogously to the procedure described above, where n and m are zero, R 1 Dimethylbutyl and R 4 Phenyl (synthesis not further elaborated).

[0214] Measurement of the oxidation induction time (OIT)

[0215] The compound according to formula (III) was investigated for its potential protective effect as an anti-aging agent or antioxidant by measuring the oxidation induction time under laboratory conditions.

[0216] For this purpose, the compound according to formula (III) and comparatively 6PPD were used together with a polymer (liquid synthetic polyisoprene (IR), LIR-50, Kuraray, weight average molecular weight distribution Mw = 54,000 g / mol, glass transition temperature T g= -63°C) at 180°C until oxidation began. The time required for this is the above-mentioned "oxidation induction time" within the meaning of the present invention.

[0217] Heat up to 180°C:

[0218] Starting temperature: 35°C, initial heating to 170°C at a heating rate of 20 K / min (Kelvin per minute), followed by further heating to 180°C at a heating rate of 1 K / min; purge gas: nitrogen (N2) at a flow rate of 50 mL / min. The sample was held isothermally at 180°C for 5 minutes under an N2 atmosphere and then switched to an O2 atmosphere (at a flow rate of 50 mL / min).

[0219] Heating to 150°C:

[0220] Heating to 150°C was carried out analogously, with heating first to 140°C at a heating rate of 20 K / min (Kelvin per minute) and then to 150°C at a heating rate of 1 K / min.

[0221] Oxidation was monitored using DSC (differential scanning calorimetry). The time until oxidation occurred was measured in minutes. The results are summarized in Table 1 in comparison to the known antioxidant 6PPD.

[0222] Table 1 , oxidation induction time in [min]

[0223] Table 1 shows that the compound according to formula (III) achieves a sufficient to good protective effect compared to 6PPD, namely approximately 75%, at the temperature of 180°C, which is considered particularly demanding. This also applies to the temperature of 150°C (approximately 71%). Thus, the overall potential protective effect can be classified as good.

[0224] The compounds of formula (I) in general, and of formula (III) in particular, are based on a phenophosphazinine or phenophosphazinine 10-oxide core structure. In comparison, 6PPD is based on a diphenylamine core structure. However, phenophosphazinine derivatives are potentially less harmful to the environment and health. Furthermore, the compound or class of compounds according to the invention achieves a completely sufficient protective effect.

[0225] The compound of the invention according to formula (III), as a representative of the compound of the invention according to formula (I), also exhibits sufficient solubility in rubber mixtures. For the (particularly preferred) application in a rubber mixture for vehicle tires, the compound of the invention according to formula (I), represented by a compound of formula (III), is added, for example, instead of the antiaging agents known in the art, such as 6PPD, 7PPD, or IPPD, in a manner known to the person skilled in the art, in one of the mixing stages during the preparation of the rubber mixture.

[0226] For this purpose, the compound according to formula (III) is mixed in various amounts (see Table 2). The resulting examples according to the invention are labeled E1 and E2.

[0227] For comparison, rubber compounds containing 6PPD instead of the compound of formula (III) as an anti-aging agent were used, with otherwise identical compositions, whereby an equal molar exchange was made between V1 and E1 and V2 and E2. The amounts in Table 2 are given in phr. Furthermore, a reference (Ref.) without anti-aging agent is given.

[0228] For all mixtures, the sum of the amounts of anti-aging agent (6PPD or compound according to formula (III)) and plasticizer oil MES is 10 phr.

[0229] Table 2, exemplary rubber compounds [phr] The examples of rubber mixtures according to the invention also show, compared to typical ones, particularly those known from the prior art,

[0230] Rubber compounds have a comparatively sufficient anti-aging effect

[0231] (Data not shown). The reference, however, shows an overall insufficient anti-aging effect.

Claims

Patent claims 1. Compound according to formula (I): (I), where - R 1 is selected from the group consisting of - xi) aromatic residues, and - xii) aliphatic C3 to C12 residues, - R 2 and R 3 are the same or different and are independently selected from the group consisting of aliphatic Ci to Ci2 residues, aromatic residues, halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether residues, - R 4 is selected from the group consisting of aliphatic Ci to Ü2o residues and aromatic Cs to C2o residues, - X means oxygen or sulfur, - m is 0 or 1 or 2 or 3, and - n is 0 or 1 or 2 or 3 or 4.

2. A compound according to claim 1, which has the structure according to formula (II): (II). where R 1, R 2 , R 3 , R 4 , X, m, and n are as defined in claim 1.

3. A compound according to claim 1 or 2, wherein n and m are identical or different, preferably identical.

4. A compound according to any one of claims 1 to 3, wherein n and m are zero.

5. A compound according to any one of claims 1 to 4, wherein R 4 is an aromatic Cs to C radical, preferably an aromatic Cs to C radical, more preferably an aromatic Cs to Cu radical, particularly preferably an aromatic Ce to Ci2 radical, most preferably an aromatic Ce to Cw radical.

6. A compound according to any one of claims 1 to 4, wherein R 4 is an aliphatic C1 to C2 radical, preferably an aliphatic C2 to C3 radical, more preferably an aliphatic C3 to C12 radical, particularly preferably an aliphatic C4 to C12 radical, most preferably an aliphatic C5 to C12 radical.

7. A compound according to any one of claims 1 to 6, wherein R 4 heptyl, octyl, nonyl, benzyl or phenyl.

8. A compound according to any one of claims 1 to 7, wherein R 1 1,3-dimethylbutyl, phenyl, benzyl or cyclohexyl, preferably 1,3-dimethylbutyl.

9. A compound according to any one of the preceding claims, having the structure according to formula (III): (St.).

10. A rubber mixture containing the compound according to any one of claims 1 to 9, preferably comprising one or more than one diene rubber.

11. Vehicle tire, preferably a pneumatic vehicle tire, which has the rubber mixture according to claim 10 in at least one component, preferably in at least one outer component, wherein the outer component is preferably a tread, a sidewall and / or a horn profile.

12. Use of the compound according to any one of claims 1 to 9 as an anti-aging agent and / or antioxidant, preferably in - vehicle tires, particularly pneumatic vehicle tires, - rubber articles other than vehicle tires, particularly preferably selected from the group consisting of air springs, bellows, bands, belts, straps, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robot applications, shoe soles and parts of a shoe sole, - oils and / or fats, and / or - Fuels and / or lubricants.

13. Use of the rubber mixture according to claim 10 for producing a - vehicle tyre, preferably a pneumatic vehicle tyre; and / or - rubber article which is not a vehicle tire, particularly preferably selected from the group consisting of air springs, bellows, bands, belts, straps, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robot applications, shoe soles and parts of a shoe sole.

14. A process for preparing a compound according to formula (I), comprising the process steps: i) preparing or providing a compound according to formula (B1): ii) Reaction of the compound according to formula (B1 ) with - hydrogen and a ketone or aldehyde, preferably a ketone, to give the compound of formula (I): (I), where - R 1 is selected from the group consisting of - xi) aromatic residues, and - xii) aliphatic C3 to C12 residues, - R 2 and R 3are the same or different and are independently selected from the group consisting of aliphatic Ci to Ci2 residues, aromatic residues, halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether residues, - R 4 is selected from the group consisting of aliphatic Ci to C2o residues and aromatic Cs to C2o residues, - X means oxygen or sulfur, - m is 0 or 1 or 2 or 3, - n is 0 or 1 or 2 or 3 or 4, and - Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, amino and nitro, preferably amino and nitro.

15. The method according to claim 14, wherein the reaction in step ii) - by means of a catalyst, and / or - at a temperature of 40 to 190°C, preferably from 55 to 170°C, particularly preferably from 70 to 150°C, especially preferably from 85 to 130°C, and / or - at a pressure of 20 to 70 bar, preferably 28 to 57 bar, particularly preferably 35 to 45 bar.

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