Compounds for use as anti-aging agents in rubber blends and vehicle tires

Abstract

The present invention relates to a compound of formula (I) (which is further defined herein), to a rubber mixture containing the compound, to a vehicle tyre comprising the rubber mixture in at least one component, to a method for producing the compound and to the use of the compound as an aging stabilizer and / or antioxidant.

Description

TECHNICAL FIELD

[0001] The present invention relates to a compound of formula (I)

[0002]

[0003] (I),

[0004] further defined herein; a rubber mixture containing the compound; a vehicle tire comprising the rubber mixture in at least one component; a process for producing the compound and the use of the compound as an aging stabilizer and / or antioxidant. BACKGROUND

[0005] Polymeric compounds, especially rubbers, are known for use in vehicle tires and in rubber articles other than vehicle tires, preferably industrial rubber articles. Natural rubber (NR) and synthetic polymers, such as IR, BR, SSBR, ESBR, etc., and also natural and synthetic oils, fats, lubricants and fuels, are subjected to oxidative reactions over a long period of storage and often in the target application at elevated temperatures, which have a detrimental effect on the initially desired properties. Depending on the type of polymer / long-chain compound, these undergo a shortening (up to liquefaction of the article), or the material / article undergoes a subsequent undesired hardening.

[0006] Aging stabilizers therefore decisively contribute to improving the durability of vehicle tires / rubber articles and the corresponding compositions.

[0007] Typical aging stabilizers include aromatic amines, such as, for example, 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 aging stabilizers can generally react with and scavenge oxygen, ozone and / or free radicals, preferably alkyl, alkoxy and alkylperoxy radicals, and thus protect the polymer / long-chain compounds, especially from undesirable oxidation and radical reactions. Aging stabilizers that react with and scavenge ozone are often also specifically referred to as "antiozonants".

[0008] However, a disadvantage of the above-mentioned compounds is that they are suspected of being carcinogenic and / or environmentally harmful.

[0009] Another problem associated with aging stabilizers is the undesired problem of blooming. Here, the slightly inferior solubility of the molecules of the aging stabilizer in the surrounding polymer matrix of the tire / rubber article causes them to diffuse to the surface of the article and often form a film there which is often distinguishable in color from the rest of the article. In the case of vehicle tires, this typically manifests itself as a brownish coloring of the otherwise black sidewall. In addition to the aesthetic disadvantage, this is also associated with a disadvantage in terms of the aging stabilization effect. This is because the already bloomed compound is typically removed or taken out of the vehicle tire by this process. This first of all reduces the total amount of aging stabilizer and also has the effect that further molecules of the aging stabilizer diffuse in the direction of the surface, thus leading to a constantly decreasing level of protection.

[0010] Aging stabilizers in rubber compositions are known. For example, US 5,140,055 A discloses imidazole and benzimidazole derivatives in rubber mixtures. SUMMARY

[0011] The object of the present application is to provide novel compounds which can be used, inter alia, as aging stabilizers in vehicle tires and / or other rubber articles, preferably industrial rubber articles, different from vehicle tires, especially with a lower potential hazard and with sufficient solubility in the respective matrix, for example and especially in polymers. This is intended to ensure a constant optimum protection from the effects of oxygen, free radicals and / or (preferably and) ozone and to minimize or even prevent the tendency to bloom, while reducing the hazard to health.

[0012] The compounds are intended to ensure at the same time at least comparable or even improved aging stabilization compared to known aromatic amines, such as 6PPD.

[0013] The problem is solved by the compounds of the formula (I) according to the application:

[0014]

[0015] (I),

[0016] wherein

[0017] - R 1 is selected from the group consisting of:

[0018] - xi) an aromatic group and

[0019] - xii) an aliphatic C3- to C 12 group,

[0020] - R 2 and R 3 are identical or different and are independently selected from the group consisting of:

[0021] aliphatic Ci- to C 12 - groups, aromatic groups, halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups,

[0022] - m is 0 or 1 or 2 or 3,

[0023] - n is 0 or 1 or 2 or 3 or 4, and

[0024] - X is an aromatic or aliphatic ring.

[0025] The compounds of formula (I) according to the application are benzimidazole derivatives and exhibit a lower potential hazard with respect to known aniline-based aging stabilizers and their decomposition products. This is a decisive advantage in vehicle tires and in rubber articles other than vehicle tires, preferably industrial rubber articles, since rubber constituents are often released by abrasion / other decomposition processes.

[0026] The compounds of formula (I) according to the application exhibit a significantly improved aging stabilization, in particular in rubber mixtures / vehicle tires, compared to the known and commonly used aging stabilizer 6PPD (see examples below), in particular.

[0027] The compounds of formula (I) according to the application are preferably antiozonants, particularly preferably also antiozonants, i.e. in addition to being able to react with oxygen and / or free radicals (preferably as mentioned above).

[0028] The compounds of formula (I) according to the application are preferably suitable as a replacement for 6PPD, the decomposition products of which are unambiguously toxic to silver salmon, and thus possibly also to other aquatic organisms.

[0029] The indices m and n describe the number of the corresponding groups R 2 and R 3 . If m or n is equal to 0 (zero), the group R 2 or R 3 is not present, but is replaced by a hydrogen atom. This is preferably the case independently. Since X is a ring which typically comprises at least several carbon atoms, R 3 is considered to be a substituent on this ring, and is either not present at all (n is equal to zero, but is hydrogen), is a single one (n is equal to 1) or is multiple (n is equal to 2 to 4) (R 2 is also the case at the benzimidazole basic structure). R 2 and R 3 are preferably optional in the compounds according to the application.

[0030] It is likewise clear to the person skilled in the art that (R2 m and NHR 1 with 4 possible bonds to carbon and (R 3 n The representation of the bond of the group X 1 is to be understood as meaning a bond to any of the possible carbon atoms in the ring X. The groups are arranged in each case at any position in the respective ring to which they are assigned, except of course two or more simultaneously at the same position. In the context of the present application, the group NHR 1 is equivalent to N(H)R 12 . That is to say, a secondary amine is involved.

[0031] In the context of the present application, the term "C3- to C 12 - group" is to be understood as meaning a group comprising 3 to 12 carbon atoms.

[0032] In the context of the present application, it is generally the case that the present application is not bound to a specific mechanism of action or a specific explanation.

[0033] The compounds of the formula (I) according to the present application have sufficient to very good solubility in rubber mixtures, in particular in rubber mixtures for vehicle tires and rubber articles other than vehicle tires, in particular industrial rubber articles. The solubility is preferably further optimized by suitable selection of the groups R 2 and / or R 3 . This minimizes or even largely prevents undesired blooming of the compounds, which in turn facilitates the aging stabilization effect. The less the aging stabilizer blooms, the less it is intentionally or unintentionally lost via the surface, and the less the aging stabilizer in turn spreads after the loss. This also has significant environmental benefits.

[0034] The present application comprises all preferred embodiments reflected in particular in the claims. The present application comprises and discloses in particular also embodiments resulting from combinations of different features (including having respective different preferred levels for these features), and thus a combination of a first feature which is described as "preferred" with a second feature which is described for example as "particularly preferred" is also encompassed and disclosed by the present application.

[0035] Furthermore, all information regarding the features of the compounds according to the present application also applies to the processes according to the present application for producing these compounds, to the rubber mixtures containing these compounds according to the present application and to the uses according to the present application.

[0036] Compounds according to the application:

[0037] Preference is given to the compounds according to the present application, wherein the compounds have the structure of the formula (II):

[0038]

[0039] (II),

[0040] wherein R 1 , R 2 , R 3 , m, n and X are as defined above, preferably as defined as preferred in the present text.

[0041] The group X is a ring or ring structure which is integrated into the overall structure. When n is zero, X is monovalent, because in this case the substituent R 3 represents hydrogen. When n is 1 or more, X is at least divalent. In this case, R 3 is at least single-bonded to the ring X.

[0042] The group X is aromatic (i.e. its carbon atoms are completely / exclusively aromatic) or aliphatic (i.e. completely / exclusively aliphatic carbon atoms). However, the group X is in each case necessarily a ring structure.

[0043] It is given preference that the compounds of formula (I) according to the application, preferably the compounds as described above and / or below as preferred, wherein X comprises 6 carbon atoms, preferably phenyl or cyclohexyl.

[0044] The aforementioned in connection with the compounds of formula (I) applies particularly preferably also in connection with the compounds of formula (II), mutatis mutandis, and vice versa. The compounds of formula (II) particularly easily achieve the objects of the present application and exhibit sufficient to good solubility in rubber mixtures, especially for vehicle tires.

[0045] It is given particular preference that the compounds according to the application, preferably the compounds as described above and / or below as preferred, wherein the compounds have the structure of formula (Ia) or (Ib)

[0046]

[0047] (Ia),

[0048]

[0049] (Ib),

[0050] wherein R 1 , R 2 , R 3 , m and n are as defined above, preferably as defined as preferred in the present text.

[0051] In compounds having formula (Ia), X is aromatic (i.e., completely aromatic), while in compounds having formula (Ib), X is aliphatic (i.e., completely aliphatic).

[0052] The compounds according to the invention are given greater preference, preferably the compounds described above and / or below as preferred, wherein the compounds have the structure of formula (IIa) or (IIb).

[0053]

[0054] (IIa),

[0055]

[0056] (IIb),

[0057] Where R 1 R 2 R 3 m and n are as defined above, preferably as defined herein.

[0058] In the context of this invention, n is generally considered to be independent of each other. This means, for example, that n in formula (Ia) / (IIa) is independent of n in formula (Ib) / (IIb). This also applies to m and all embodiments of the compounds according to the invention.

[0059] In the context of this invention, a further case is that R 2 They are independent of each other. This means, for example, R in equation (Ia) / (IIa) 2 Independent of R in equation (Ib) / (IIb) 2 This applies equally to R. 3 And all embodiments of the compounds according to the present invention. 2 and R 3 They are also independent of each other in principle.

[0060] In the compounds according to the invention, preferably as described above and / or below as preferred, the group R 2 and R 3 They are either the same or different and are independently selected from the following groups: aliphatic C1- to C 12 - Groups, aromatic groups, halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups.

[0061] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 Aliphatic C1-to-C12 - The group independently comprises a straight-chain portion, a branched portion, and / or a cyclic portion; preferably straight-chain, branched, or cyclic.

[0062] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 Aliphatic C1-to-C 12 - The functional group is independently saturated or unsaturated, preferably saturated.

[0063] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 The aliphatic groups in it are aliphatic C1- to C1-. 10 - Group, preferably aliphatic C1- to C8- groups, more preferably aliphatic C1- to C6- groups, particularly preferably aliphatic C1- to C4- groups, very particularly preferably aliphatic C1- to C2- groups, preferably methyl and / or ethyl.

[0064] In some cases, compounds according to the invention are preferred, preferably compounds as described above and / or below as preferred, wherein R 2 and R 3 Aliphatic C1-to-C 12 - The group independently represents one or more halogen substituents, which are preferably selected from the group consisting of fluorine, chlorine and bromine.

[0065] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 The aromatic groups in the aromatic group independently contain 5 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, particularly preferably 6 to 10 carbon atoms, and most preferably 6 to 8 carbon atoms.

[0066] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 The aromatic group in the figure independently represents one or more halogen substituents, which are preferably selected from the group consisting of free fluorine, chlorine and bromine.

[0067] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 The halogen groups are independently selected from the group consisting of fluorine, chlorine, and bromine.

[0068] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 The ester group, ketone group, ether group, and thioether group in the form 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 particularly preferably 1 to 7 carbon atoms, and most preferably 1 to 5 carbon atoms. In some cases, it is preferred to combine the upper limit of the above-mentioned carbon atoms with the lower limit of at least 2 carbon atoms.

[0069] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 2 and R 3 Independently comprising at most 12 carbon atoms, preferably 10 carbon atoms, particularly preferably 6 carbon atoms, and very particularly 4 carbon atoms. This should be understood to mean, for example, R 3 It has at most 10 carbon atoms, while R 2 It has a maximum of 6 carbon atoms.

[0070] The listed groups R 2 and R 3 Particularly preferred is that it has been attached by selecting a suitable starting compound.

[0071] The preferred compounds are those according to the invention, preferably those described above and / or below, wherein n and m are different or the same.

[0072] Substituent R 2 and R 3 The number and type (if chosen) have a decisive influence on the solubility of the compounds according to the invention in rubber mixtures according to the invention and vehicle tires according to the invention.

[0073] The preferred embodiment is the compound according to the invention, wherein in formula (Ia) and / or (IIa), m is zero and n is 1, and preferably R 3 It is an aliphatic C1-to-C 12 - group. With R 3 The foregoing description relating to its particularly preferred embodiments is preferably applicable accordingly. In many cases, such preferred compounds exhibit improved solubility in rubber mixtures according to the invention, and thus achieve the essential purpose particularly well. This further reduces or even completely prevents undesirable blooming.

[0074] The preferred embodiment is the compound according to the invention, wherein m and n are zero in formula (Ib) and / or (IIb). The cyclohexyl group already present in the compound (for X) also ensures improved solubility in the rubber mixture according to the invention. In this case, the R group can be preferably omitted. 3 Additional substituents in the form of [formula missing].

[0075] In the context of this invention, compounds according to the invention are particularly preferred, wherein the compounds have the structure of formula (IIa-I):

[0076]

[0077] (IIa-I)

[0078] in

[0079] - R 1 It is an aliphatic C3-to-C 12 -Group, preferably C4- to C8-alkyl,

[0080] - R 2 and R 3 They are either the same or different and are independently selected from the following groups:

[0081] Hydrogen, aliphatic C1- to C 12 - Groups, aromatic groups, halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups; preferably hydrogen and aliphatic C1- to C1- groups. 12 - group.

[0082] The foregoing content (and the following) relating to the compounds according to the invention and their preferred embodiments is preferably also applicable, with necessary modifications, to the preferred compounds having formula (IIa-I).

[0083] In the compounds according to the present invention, the group R 1 Choose from the following groups:

[0084] - xi) Aromatic groups and

[0085] - xii) Aliphatic C3-to-C 12 - group.

[0086] In some cases, compounds according to the invention are preferred, preferably compounds as described above and / or below as preferred, wherein the aromatic group in xi) encompasses substituents selected from the group consisting of alkyl, halogen, cyano, ester, ketone, ether, and thioether groups; particularly preferred are alkyl, ester, ketone, ether, and thioether groups. In other cases, and particularly preferably, the aromatic group in xi) does not contain the aforementioned substituents, and preferably is not substituted at all. Substituents are preferably in the meta or para position. Substituents are particularly preferably not in the ortho position. This is particularly advantageous for the lifespan of the aging stabilizer.

[0087] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein the aromatic group in xi) comprises 5 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, and most preferably 6 to 8 carbon atoms.

[0088] Particularly preferred are compounds according to the invention, preferably as described above and / or below, wherein the aromatic group in xi) includes phenyl (i.e., –C6H5), α-methylbenzyl (i.e., –CH2(CH3)-C6H5) and / or benzyl (i.e., –CH2–C6H5), with phenyl being particularly preferred.

[0089] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein the aliphatic C3- to C4- of xii) are... 12 - The group comprises a straight-chain portion, a branched portion, and / or a cyclic portion; preferably straight-chain, branched, or cyclic, and most preferably branched.

[0090] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein the aliphatic C3- to C4- of xii) are... 12 - The functional group is saturated or unsaturated, preferably saturated.

[0091] Particularly preferred are compounds according to the invention, preferably as described above and / or below, wherein in xii), the aliphatic group is aliphatic C3- to C4-. 10 - Group, preferably aliphatic C4- to C8- group, more preferably aliphatic C5- to C7- group.

[0092] The preferred compounds are those according to the invention, preferably those described above and / or below as preferred, wherein R 1 Contains tertiary carbon atoms, R 1 The tertiary carbon atom is bonded to a nitrogen atom (N). The nitrogen atom (N) is preferably a secondary nitrogen atom.

[0093] In the context of this invention, the term "tertiary carbon atom" should be understood to mean a carbon atom having only one hydrogen atom bonded to it. This produces a particularly good protective effect compared to secondary and quaternary carbon atoms, preferably in rubber blends (particularly preferred for vehicle tires and / or other rubber products (especially industrial rubber products)). In particular, optimized reactivity is achieved within the context of mechanisms related to aging stability, where undesirable side reactions are avoided.

[0094] Particularly preferred are the compounds according to the invention, wherein R 1 The branched or cyclic alkyl groups preferably contain 3 to 12 carbon atoms in each case, more preferably 3 to 8 carbon atoms in each case, and particularly preferably 4 to 7 carbon atoms in each case. These are particularly preferably saturated. For cyclic alkyl groups, it is preferred that they contain at least 5 carbon atoms, more preferably at least 6. This minimum number is preferably combined with the aforementioned upper limit for carbon atoms.

[0095] The compounds according to the invention are given a very particular preference, preferably the compounds described above and / or below as preferred, wherein R 1 It is 1,3-dimethylbutyl, phenyl, benzyl, or cyclohexyl, preferably 1,3-dimethylbutyl. This achieves particularly good protective effects in rubber blends, especially in rubber blends used in vehicle tires and rubber blends used in rubber products other than vehicle tires (preferably industrial rubber products).

[0096] The compounds according to the invention are given a very particular preference, wherein the compounds have the structure of formula (III):

[0097]

[0098] (III).

[0099] Compounds having formula (III) exhibit sufficient solubility in polymers, preferably in rubber blends, and particularly preferably in rubber blends for vehicle tires and rubber products other than vehicle tires (preferably industrial rubber products). Furthermore, compounds having formula (III) can be produced in a relatively simple, energy-efficient, and cost-effective manner, and show significantly improved protective effects compared to 6PPD (see examples below). According to IUPAC nomenclature, compounds having formula (III) according to the present invention are also called N-(1,3-dimethylbutylamino)-2-phenyl-1H-benzo[d]imidazol-6-amine.

[0100] Rubber mixtures comprising a compound of formula (I):

[0101] The present invention further relates to a rubber mixture containing the compounds according to the invention as described above (preferably as described above and / or below), and preferably containing one or more diene rubbers. The rubber mixture contains one or more compounds according to the invention, wherein it is preferred when at least one rubber is a diene rubber.

[0102] The foregoing content relating to the compounds according to the invention, especially as described above as preferred, is preferably also applicable, with necessary modifications, to the rubber mixtures according to the invention.

[0103] Therefore, the rubber mixture according to the invention contains at least one type of rubber. The rubber mixture according to the invention is, in principle, any rubber mixture in which the compound according to the invention acts as a low-toxicity aging stabilizer and / or anti-ozone agent. The rubber mixture according to the invention comprises one or more types of rubber.

[0104] Particularly preferred are rubber mixtures according to the invention, preferably as described above and / or below, which contain one or more compounds according to the invention, preferably as described above and / or below, particularly preferably selected from the group consisting of compounds having formulas (I), (Ia), (Ib), (II), (IIa), (IIb), (IIa-I), and (III), particularly preferably containing compounds having formulas (IIa-I) and / or (III).

[0105] Preferred are rubber mixtures according to the invention, preferably as described above and / or below, which contain one or more compounds according to the invention (preferably as described above), wherein these are the only benzimidazole compounds in the rubber mixture, and particularly preferably compounds having formula (IIa-I) or (III) are the only benzimidazole compounds in the rubber mixture.

[0106] The preferred embodiment is a rubber mixture according to the invention, preferably as described above and / or below, which contains a total amount of the compound according to the invention in the amount of 0.1 to 10 phr, preferably 0.3 to 8 phr, more preferably 0.6 to 6 phr, particularly preferably 0.8 to 4.5 phr, and very particularly preferably 1 to 3 phr.

[0107] In the context of this invention, the unit "phr" (parts per hundred parts by weight of rubber) is a unit of measurement for quantities in conventional rubber industry compound formulations. A part by weight dosage is based on 100 parts by weight of all high molecular weight (M) components present in the compound. wThe total mass of rubber (greater than 20,000 g / mol).

[0108] The rubber mixtures according to the invention, preferably as described above and / or below, preferably contain one or more diene rubbers. Diene rubbers are typically understood to mean rubbers formed by the polymerization or copolymerization of dienes and / or cycloolefins, and therefore having C=C double bonds in the main chain or in the side groups.

[0109] Preferred rubber mixtures according to the invention, preferably as described above and / or below, 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, and rubbers having a molecular weight M greater than 20,000 g / mol. w Liquid rubber, butyl rubber (IIR), halogenated butyl 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.

[0110] 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 / or "non-Hevea" sources. Preferred non-Hevea sources are guarana shrubs and dandelions. Particularly preferred dandelion is TKS (Taraxacum Kok-saghyz; Russian dandelion).

[0111] Particularly preferred are the rubber mixtures according to the invention, preferably as described above and / or below, 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 halogenated butyl rubber (XIIR).

[0112] The rubber mixtures according to the invention are particularly preferred, and preferably as described above and / or below, 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).

[0113] Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber (IIR), halogenated butyl rubber (XIIR), and / or ethylene-propylene-diene rubber are preferably used in the production of rubber products other than vehicle tires (but are also typically considered as industrial rubber products), and are preferably used in belts, drive belts, hoses, belts, and / or shoe soles. Preferably, mixtures of these rubbers that are specific to those skilled in the art in terms of fillers, plasticizers, vulcanization systems, and additives are used herein.

[0114] Polyisoprene preferably encompasses cis-1,4-polyisoprene and / or 3,4-polyisoprene. This is preferably applicable, whether involving natural or synthetic polyisoprene. Particularly preferred are cis-1,4-polyisoprene having a cis-1,4 content greater than 90% by weight. Such polyisoprene is preferably obtained by stereo-directional polymerization in solution with a Ziegler-Natta catalyst or using finely dispersed alkyl lithium. Furthermore, natural rubber (NR) is also such a cis-1,4-polyisoprene. Therefore, particularly preferred are natural rubber (NR) containing cis-1,4-polyisoprene (preferably having a cis-1,4 content of not less than 99% by weight).

[0115] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below, which contains one or more natural polyisoprene (NR) and one or more synthetic polyisoprene (IR). Therefore, a mixture containing polyisoprene is preferred.

[0116] In some cases, a particularly preferred rubber compound according to the invention, preferably as described above and / or below, is given, which contains one or more 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, and more preferably 95 to 100 phr. Such a rubber compound exhibits particularly optimized tear and abrasion properties, as well as good processability and reversion stability. A further preferred total amount is in the range of 56 to 100 phr, preferably 80 to 100 phr, and more preferably 90 to 100 phr.

[0117] In some cases, a rubber blend according to the invention is preferred, preferably as described above and / or below, comprising one or more natural polyisoprene (NR) wherein the total amount is significantly less than 100 phr. In these cases, the rubber blend additionally comprises one or more rubbers different from natural polyisoprene, preferably additional diene rubbers, 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). In these cases, a rubber blend according to the invention is particularly preferred, comprising one or more natural polyisoprene (NR) wherein the total amount is 5 to 55 phr, preferably 5 to 35 phr, more preferably 5 to 25 phr, and very particularly preferably 5 to 20 phr. Such a rubber blend exhibits particularly good processability and reversion stability, as well as optimized tear properties and optimal rolling resistance characteristics.

[0118] In some cases, a rubber compound according to the invention is preferred, preferably as described above and / or below, comprising at least one butadiene rubber (BR, polybutadiene). Preferred compounds are butadiene rubbers comprising high-cis and / or low-cis types, wherein 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. Particularly preferred low-cis types include Li-BR (lithium-catalyzed butadiene rubber), preferably having a cis content of 20% to 50% by weight. High-cis types are particularly preferred because this achieves particularly good properties, especially low hysteresis in the rubber compound.

[0119] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below, wherein one or more functional groups are used to functionalize the butadiene rubber end groups and / or along the polymer chain. It is preferred when one or more functional groups are independently selected from the group consisting of: hydroxyl, ethoxy, epoxy, siloxane, amino, aminosiloxane, carboxyl, phthalocyanine, and silane-sulfide groups. However, the selection of functional groups is preferably not limited to the above groups. In some cases, the functional groups preferably contain one or more metals.

[0120] Preferred materials include rubber blends according to the invention, preferably as described above and / or below, which contain one or more butadiene rubbers in a total amount of 10 to 80 phr, preferably 12 to 50 phr, and particularly preferably 15 to 40 phr. This achieves particularly good tear and abrasion properties and optimal braking characteristics in the rubber blends according to the invention.

[0121] In some cases, a rubber mixture according to the invention is preferred, preferably as described above and / or below, which comprises at least one styrene-butadiene rubber (styrene-butadiene copolymer). A styrene-butadiene rubber comprising one or more solution-polymerized styrene-butadiene rubbers (SSBR) and / or one or more emulsion-polymerized styrene-butadiene rubbers (ESBR) is also preferred. In the context of this 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, wherein the styrene-butadiene rubber is end-functionalized and / or functionalized along the polymer chain by one or more functional groups. For preferred functional groups, the foregoing descriptions related to butadiene rubber apply accordingly.

[0122] Preferred rubber mixtures according to the invention, and more preferably as described above and / or below, contain at least one styrene-butadiene rubber (SSBR) in a total amount of 10 to 80 phr, preferably 30 to 75 phr, and particularly preferably 50 to 70 phr. Particularly preferred rubber mixtures according to the invention contain one or more solution-polymerized styrene-butadiene rubber (SSBR) additionally present in a total amount of 10 to 80 phr, preferably 30 to 75 phr, and particularly preferably 50 to 70 phr. This achieves particularly good rolling resistance characteristics in the rubber mixtures of the invention. Particularly preferred is the use of a combination of solution-polymerized styrene-butadiene rubber (SSBR) with one or more other rubbers. This typically achieves improved and balanced characteristic profiles.

[0123] In addition to one or more compounds according to the invention and at least one rubber, the rubber mixture according to the invention preferably contains additional components, preferably at least one filler.

[0124] Preferred materials include rubber blends according to the invention, preferably rubber blends as described above and / or below, which additionally contain one or more fillers, preferably in a total quantity of 30 to 500 phr, more preferably 50 to 400 phr, and more preferably 80 to 300 phr. Particularly preferred fillers are reinforcing fillers selected particularly preferably from the group consisting of carbon black and silica.

[0125] Suitable carbon blacks generally include any type of carbon black known to those skilled in the art. Preferably, the carbon black is selected from the group consisting of industrial carbon black and pyrolytic carbon black, with industrial carbon black being preferred.

[0126] Carbon black is preferred when it has an iodine value (also known as iodine adsorption value) according to ASTM D 1510 in the range of 30 to 250 g / kg, preferably 35 to 215 g / kg, particularly preferably 40 to 180 g / kg, and very particularly preferably 45 to 140 g / kg, and / or a DBP value according to ASTM D 2414 in the range of 30 to 200 ml / 100 g, preferably 70 to 170 ml / 100 g, and particularly preferably 90 to 140 ml / 100 g. The DBP value according to ASTM D 2414 determines the specific absorption volume of carbon black or light-colored filler using dibutyl phthalate. The use of this carbon black in rubber compounds according to the invention, especially rubber compounds for vehicle tires, typically ensures the best possible trade-off between abrasion resistance and heat buildup, which in turn affects environmentally relevant rolling resistance. Carbon black with an iodine value in the range of 80 to 110 g / kg and a DBP value in the range of 100 to 130 ml / 100 g is particularly preferred. Carbon black of the N339 type is very particularly preferred.

[0127] In some cases, a preferred embodiment is a rubber compound according to the invention, preferably as described above and / or below, wherein the carbon black in the rubber compound is present in a total amount ranging from 0.1 to 60 phr, preferably 3 to 40 phr, particularly preferably 4 to 30 phr, and very particularly preferably 5 to 15 phr. In these amounts, the carbon black typically exists as a supplementary filler in combination with the primary filler, preferably one or more types of silica, and particularly preferably silica.

[0128] In other cases, a preferred embodiment is a rubber mixture according to the invention, preferably as described above and / or below, wherein carbon black is present in the rubber mixture in a total amount ranging from 30 to 300 phr, preferably 35 to 200 phr, and particularly preferably 40 to 100 phr. In these amounts, carbon black is present, in particular, as the sole filler or as the main filler (based on a total filler content greater than 50% by weight, preferably in combination with a relatively small amount of silica).

[0129] Silica is preferably amorphous silica and / or pyrolytic silica. Particularly preferred amorphous silica includes precipitated silica, also known as precipitated silica.

[0130] Particularly preferred is amorphous silica, preferably precipitated silica, having a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) in the range of 35 to 400 m² / g, preferably 50 to 350 m² / g, particularly preferably 85 to 320 m² / g, and very particularly preferably 120 to 235 m² / g, and / or (preferably) having a CTAB surface area (according to ASTM D 3765) in the range of 30 to 400 m² / g, preferably 50 to 330 m² / g, particularly preferably 80 to 300 m² / g, and very particularly preferably 115 to 200 m² / g. Such silica, for example, produces particularly good physical properties of vulcanized rubber in rubber compounds used for tire treads. Advantages in compound processing can also be achieved by reducing mixing time while retaining the same product properties, leading to increased productivity. Particularly preferred are ultrasil® VN3 type (trade name) silica from Evonik, and highly dispersible silica (so-called HD silica). Preferred highly dispersible silica includes Zeosil® 1165 MP from Solvay.

[0131] In some cases, a preferred rubber compound according to the invention, preferably as described above and / or below, is given, which contains at least one silica, preferably in a total amount in the range of 30 to 500 phr, more preferably 50 to 400 phr, and particularly preferably 80 to 300 phr. In these amounts, silica is present, in particular, as the sole filler or as the main filler (based on a total filler content greater than 50% by weight; preferably in combination with a relatively small amount of carbon black).

[0132] In some cases, a preferred rubber compound according to the invention, preferably as described above and / or below, is given, which contains at least one silica, preferably in a total amount in the range of 5 to 100 phr, more preferably 7 to 80 phr, and particularly preferably 10 to 60 phr. In these amounts, silica is typically present as a supplementary filler in combination with the main filler, preferably carbon black.

[0133] Particularly preferred are rubber mixtures according to the invention, preferably as described above and / or below, which contain at least one silica and at least one carbon black, wherein the total amount of silica is in the range of 50 to 300 phr, preferably 80 to 200 phr, and the total amount of carbon black is in the range of 5 to 60 phr, preferably 7 to 40 phr.

[0134] The rubber compound according to the invention, preferably as described above and / or below, preferably contains additional fillers, i.e., fillers that are different from / do not include carbon black, silica, and silica. These additional fillers preferably also include reinforcing fillers and / or non-reinforcing fillers.

[0135] Preferred non-reinforcing fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide, rubber gel, and / or fibers. Preferred fibers include aramid fibers, glass fibers, carbon fibers, and / or cellulose fibers.

[0136] Preferred additional reinforcing fillers include carbon nanotubes, graphite, graphene, and / or so-called "silicon carbide biphase fillers". Carbon nanotubes preferably comprise unmodified and / or functionalized carbon nanotubes, wherein the preferred functional groups are selected from the group consisting of hydroxyl, carboxyl, and carbonyl groups.

[0137] In the context of this invention, zinc oxide is not a filler used for the purposes of this invention.

[0138] Preferred materials include rubber mixtures according to the invention, preferably as described above and / or below, which contain one or more additional additives. Such additives are typically conventional additives added in typical amounts, preferably during at least one major mixing stage in the production process of the rubber mixture.

[0139] One or more additional additives preferably include:

[0140] a) An aging stabilizer, which is from the prior art and is different from compounds of formula (I) according to the invention and any other compounds according to the invention; preferably comprising p-phenylenediamine and / or dihydroquinoline, 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'-xylyl-p-phenylenediamine (DTPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), and 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ);

[0141] b) An activator, preferably comprising zinc compounds (including zinc complexes) and / or fatty acids, particularly preferably zinc oxide, stearic acid and / or zinc ethylhexanoate;

[0142] c) A reagent for binding fillers (especially for carbon black and silica), preferably comprising S-(3-aminopropyl)thiosulfate, its metal salt (especially for binding to carbon black) and / or silane coupling agents (especially for binding to silica, especially silica).

[0143] d) Anti-ozone wax;

[0144] e) Resins, especially tackifying resins;

[0145] f) A plasticizing aid, preferably comprising 2,2'-dibenzoamide diphenyl disulfide (DBD);

[0146] g) Processing aids, preferably comprising fatty acid esters and / or metal soaps, wherein preferred metal soaps include zinc soaps and / or calcium soaps, and / or

[0147] h) Plasticizers, preferably comprising oils (preferably aromatic, cycloalkane, and / or alkane mineral oils), resins, and / or liquid polymers, particularly preferably comprising MES (mild extraction solvates), DAE (distillate aromatic extracts), RAE (residual aromatic extracts), TDAE (treated distillate aromatic extracts), rubber conversion liquid oil (RTL), biomass conversion liquid oil (BTL) (preferably having a polycyclic aromatic hydrocarbon content of less than 3% by weight according to method IP 346), triglycerides (preferably rapeseed oil), ointments, hydrocarbon resins, and / or liquid polymers having a number average molecular weight (determined by GPC=gel permeation chromatography based on BS ISO 11344:2004) between 500 and 20,000 g / mol. When mineral oils are used, the mineral oils are preferably selected from the group consisting of: DAE (distillate aromatic extracts), RAE (residual aromatic extracts), TDAE (treated distillate aromatic extracts), MES (mild extraction solvents), and cycloalkane oils.

[0148] In most cases, a particularly preferred rubber compound according to the invention, preferably as described above and / or below, is rubber compound that is substantially free of, preferably not containing, 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), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD) and optionally also free of 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), more preferably substantially free of, preferably not containing p-phenylenediamine and optionally also free of dihydroquinoline, and most preferably substantially free of, preferably not containing aging stabilizers other than those of the compounds according to the invention (i.e., conventional aging stabilizers known from the prior art). Therefore, it is particularly preferred that the rubber mixture according to the invention contains one or more compounds according to the invention, preferably as described above as preferred, as the sole aging stabilizer. In the context of the invention, "substantially free of" should be understood to mean an upper limit of 0.1 phr, preferably in the range of 0 phr to 0.1 phr, particularly preferably 0.0001 phr to 0.1 phr. A quantity of zero (0), i.e., "not containing", is particularly preferred. These very preferred small amounts (including zero (0) phr) allow for comparable protective effects with significantly reduced toxicity. The compounds according to the invention replace the typically used p-phenylenediamine known in the prior art. In some other cases, it is preferred that the rubber mixture according to the invention contain aging stabilizers (especially p-phenylenediamine) other than the compounds according to the invention, which have been at least partially replaced by one or more compounds according to the invention, preferably up to 50% or more by weight. This has at least partially achieved the advantages according to the invention, although not to the optimal extent.

[0149] As defined above, the absence of additional dihydroquinoline, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), is optional, i.e., desirable in some cases and undesirable in others. In some cases, a rubber compound according to the invention is preferred, preferably as described above and / or below, which contains (whether or not p-phenylenediamine) one or more dihydroquinoline, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ). It is preferred when the rubber compound according to the invention contains a total amount of dihydroquinoline, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), in the range of 0.1 to 3 phr, preferably 0.5 to 1.5 phr.

[0150] Anti-ozone wax (see above d) is considered separately and is preferably present in the rubber mixture according to the invention, regardless of the presence of the aging stabilizer according to a).

[0151] Silane coupling agents (see c above) preferably include all types known to those skilled in the art. Rubber mixtures according to the invention, preferably as described above and / or below, preferably contain one or more silane coupling agents. In some cases, rubber mixtures according to the invention preferably contain a mixture of different silanes.

[0152] Silane coupling agents react with the surface silanol groups or other polar groups of silica (especially silica) during the mixing of rubber / rubber mixtures (in situ) or before they are added to the rubber during pretreatment (pre-modification).

[0153] Preferred silane coupling agents include bifunctional organosilanes having at least one alkoxy, cycloalkoxy, or phenoxy group as a leaving group on a silicon atom, and optionally containing (after dissociation) additional functional groups capable of undergoing a chemical reaction with the double bond of the polymer. Preferred functional groups include -SCN, -SH, -NH2, and / or -S. x - (where x = 2 to 8). Silanes having the -SH group are typically also called mercaptosilanes. Preferred mercaptosilanes include terminally capped mercaptosilanes, preferably according to WO 99 / 09036 A1.

[0154] Particularly preferred silane coupling agents include 3-mercaptopropyltriethoxysilane, 3-thiocyanopropyltrimethoxysilane, and mixtures of 3,3'-bis(triethoxysilylpropyl) polysulfides (particularly preferred 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT) and / or its disulfide (TESPD)) and / or sulfides having 2 to 8 sulfur atoms, preferably each having a different number of sulfur atoms. In some cases, TESPT is preferred, particularly preferably in the form of a mixture with industrial carbon black (from Evonik's trade name X50S®).

[0155] Alternatively or additionally, preferred silane coupling agents also include those according to WO 2008 / 083241 A1, WO 2008 / 083242 A1, WO 2008 / 083243 A1 and / or WO 2008 / 083244 A1. Alternatively or additionally, further preferred silane coupling agents include silanes (preferably 3-octanoylthio-1-propyltriethoxysilane) sold by Momentive, USA under the name NXT in various variants and / or silanes sold by Evonik Industries under the name VP Si 363®.

[0156] The preferred embodiment is a rubber mixture according to the invention, preferably as described above and / or below, wherein one or more additional additives are present in a total amount in the range of 3 to 150 phr, preferably 4 to 100 phr, more preferably 5 to 80 phr.

[0157] Preferred materials include rubber mixtures according to the invention, preferably rubber mixtures as described above and / or below, which contain one or more activators (see b above)), preferably zinc compounds, and particularly preferably zinc oxide. Preferably, there is no limitation on the type of zinc oxide. Preferred materials are granules and / or powders. The zinc oxide preferably has a BET surface area of ​​up to 100 m² / g, preferably in the range of 1 to 100 m² / g. In some cases, zinc oxide is preferred where the BET surface area is less than 10 m² / g. In other cases, zinc oxide is preferred where the BET surface area is in the range of 10 to 100 m² / g, and so-called "nano zinc oxide" is particularly preferred.

[0158] Preferred rubber compounds according to the invention, preferably as described above and / or below, are vulcanized or partially vulcanized, preferably vulcanized. This means that they are preferably used in a vulcanized or partially vulcanized state, particularly preferably in vehicle tires or rubber articles other than vehicle tires (preferably industrial rubber articles). In the context of this invention, the terms "vulcanized" and "crosslinked" are used synonymously. Therefore, the rubber compounds according to the invention are preferably crosslinked rubber compounds. However, it goes without saying that, to those skilled in the art, rubber compounds are typically in vulcanized form until final processing.

[0159] The vulcanization of the rubber compound according to the invention is preferably carried out in the presence of sulfur and / or sulfur donors, preferably in the presence of vulcanization accelerators, some of which are also sulfur donors.

[0160] Preferred materials include rubber mixtures according to the invention, preferably as described above and / or below, which contain sulfur and / or one or more sulfur donors. There are no particular limitations regarding the sulfur donors, and therefore, the sulfur donors considered in principle include all sulfur donors known to those skilled in the art, provided they are available in a suitable form under existing conditions.

[0161] Preferred is the rubber compound according to the invention, which contains (or alternatively, in addition to a sulfur donor) one or more vulcanization accelerators.

[0162] Preferred vulcanization accelerators include thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate ester accelerators, and / or guanidine accelerators. Particularly preferred are one or more sulfenamide accelerators and / or one or more guanidine accelerators, and very particularly one or more accelerators 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 diphenylguanidine (DPG).

[0163] Preferred rubber compounds according to the invention, preferably as described above and / or below, contain one or more vulcanization retarders. The presence of a vulcanization retarder contributes, for example, to the progress of a better balance in vulcanization.

[0164] The rubber compound according to the invention is preferably produced or supplied, and particularly preferably produced. This is preferably accomplished by methods conventional in the rubber industry, wherein a base mixture comprising all components except for the vulcanization system (i.e., excluding the vulcanization system) is initially provided in one or more mixing stages, wherein the vulcanization system comprises sulfur and compounds that affect vulcanization, i.e., preferably sulfur, sulfur donors, vulcanization accelerators, and vulcanization retarders in total. The vulcanization system is added in the final mixing stage to produce a final mixture, which is preferably subjected to further processing by extrusion and / or calendering and is shaped into the desired form. The shape thus achieved preferably determines the subsequent use, such as in vehicle tires.

[0165] It is preferred that the rubber mixture according to the invention be used in vulcanized rubber.

[0166] A greater preference is given to the use of the rubber compound according to the invention in vehicle tires, preferably in the external or internal parts of vehicle tires, preferably in the external parts.

[0167] Preferred materials are rubber mixtures according to the invention, preferably as described above and / or below, which contain one or more strength members, which preferably contain fibers, fabrics and / or cords.

[0168] Vehicle tire comprising a rubber mixture according to the application:

[0169] The present invention further relates to a vehicle tire, preferably a pneumatic vehicle tire, which includes, in at least one component, preferably in at least one external component, a rubber compound according to the invention as described above, preferably as described above as preferred, wherein the external component is preferably a tread, sidewall, and / or flange profile.

[0170] The foregoing content (including preferred embodiments in each case) relating to the compounds and rubber mixtures according to the invention is preferably also applicable to vehicle tires according to the invention, with necessary modifications.

[0171] The vehicle tires according to the invention are preferably vulcanized, i.e., not green tires. The vulcanized vehicle tires preferably contain at least one vulcanized rubber of the rubber compound according to the invention in at least one component. It is known to those skilled in the art that most compounds (e.g., existing rubbers) are present in a chemically modified form, or may be present only after mixing or only after vulcanization.

[0172] The vehicle tires according to the present invention, preferably as described above and / or below, preferably include pneumatic vehicle tires and / or solid rubber tires.

[0173] The vehicle tires according to the present invention, preferably as described above and / or below, are preferably selected from the group consisting of industrial and construction vehicle tires, truck tires, passenger car tires and two-wheeled vehicle tires.

[0174] Particularly preferred are vehicle tires according to the invention, preferably as described above and / or below, which contain a rubber compound according to the invention in two, three or more components.

[0175] Use of a compound according to the application and of a rubber mixture according to the application:

[0176] The present invention very generally relates to the use of compounds according to the invention, preferably as described above as preferred, in rubber mixtures, and preferably in rubber mixtures according to the invention (preferably as described above as preferred), as aging stabilizers and / or (preferably) antioxidants.

[0177] The present invention further relates to the use of compounds according to the invention as described above, preferably as above and / or below, as preferably used as aging stabilizers and / or antioxidants (preferably as aging stabilizers):

[0178] - Vehicle tires, especially pneumatic vehicle tires;

[0179] - Unlike rubber products for vehicle tires, these are particularly preferably selected from the group consisting of: air springs, bellows, belts, drive belts, hoses, profiles, seals, films, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and sole parts;

[0180] - Oils and / or greases; and / or

[0181] - Fuel and / or lubricant.

[0182] The foregoing description of the compounds (including preferred embodiments) and rubber mixtures (including preferred embodiments) according to the invention, preferably with necessary modifications, also applies to their use as aging stabilizers and / or antioxidants according to the invention.

[0183] Preferred belts include conveyor belts.

[0184] In some cases, the use of the compounds according to the invention as aging stabilizers and / or antioxidants in oils, greases, fuels and / or lubricants is preferred, particularly in the context of use in engines.

[0185] The present invention also relates to rubber mixtures according to the invention, preferably rubber mixtures as described above and / or below, for the production of the following uses:

[0186] - Vehicle tires, preferably pneumatic vehicle tires, and / or

[0187] - Unlike rubber products for vehicle tires, these are particularly preferably selected from the group consisting of: air springs, bellows, belts, drive belts, hoses, profiles, seals, films, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and sole parts.

[0188] The foregoing description of the compounds (including preferred embodiments) and rubber mixtures (including preferred embodiments) according to the invention, preferably with necessary modifications, also applies to the uses according to the invention as described above. The following description, preferably with necessary modifications, also applies to vehicle tires according to the invention.

[0189] Preferred uses are for producing any tire component (including external and / or internal components), preferably for producing external components, and particularly preferably for producing flange profiles, treads, and / or sidewalls. Particularly preferred uses are for producing the crown layer of a tread with a crown / base structure. Different forming processes during extrusion / calendering preferably determine the type of component. Preferred internal components include rubber rollers, liners, core profiles, belts, shoulders, belt profiles, carcasses, bead reinforcements, bead profiles, and / or bands. The rubber compound used for internal components is typically also referred to as the body compound. Different components, having different shapes and in an unvulcanized state, are typically used in the construction of the green tire. The unvulcanized green tire is then preferably vulcanized.

[0190] The invention also relates to the production of rubber articles that differ from vehicle tires. These rubber articles preferably have a construction consisting of multiple layers, and particularly preferably one or more layers include at least one strength member.

[0191] Preferred belts include rubber belts and / or transmission belts.

[0192] Process for producing a compound according to the application:

[0193] The present invention further relates to a method for producing compounds according to the invention, preferably compounds having formula (I), the method comprising the following steps:

[0194] i) Producing or supplying compounds having formula (B1):

[0195]

[0196] (B1),

[0197] ii) React the compound having formula (B1) with the following:

[0198] - Hydrogen and ketones or aldehydes, preferably ketones,

[0199] To obtain the compound having formula (I):

[0200]

[0201] (I),

[0202] in

[0203] - R 1 Choose from the following groups:

[0204] - xi) Aromatic groups and

[0205] - xii) Aliphatic C3-to-C 12- group,

[0206] - R 2 and R 3 They are either the same or different and are independently selected from the following groups:

[0207] Aliphatic C1-to-C 12 - Groups, aromatic groups, halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups,

[0208] - m can be 0, 1, 2, or 3.

[0209] - n can be 0, 1, 2, 3, or 4.

[0210] - X is an aromatic or aliphatic ring, and

[0211] - Z is selected from the group consisting of: halogens, sulfonates, leaving groups based on sulfonates, amino and nitro groups, preferably amino and nitro groups.

[0212] The foregoing content relating to the compounds according to the invention (preferably and especially as defined above as preferred) also applies, preferably with necessary modifications, to the production methods according to the invention. This means that all the foregoing content relating to the description of the compounds according to the invention (including preferred embodiments) and taking into account each preferred level and the possibility of combinations of these features applies to R. 1 R 2 R 3 X, m, and n.

[0213] When the halogen in Z includes chlorine, bromine, or iodine, chlorine is preferred. When fluorine is not included, it is particularly preferred.

[0214] When the leaving group based on sulfonate esters in Z includes trifluoromethanesulfonate, perfluorobutanesulfonate, methanesulfonate or toluenesulfonate, it is preferred.

[0215] Z is very preferably a nitro or amine. This means that the very preferred starting compound is the corresponding aminobenzimidazole or nitrobenzimidazole, wherein X is particularly preferably a phenyl ring or a cyclohexyl ring. Therefore, the foregoing is particularly applicable to compounds having formulas (Ia), (Ib), (IIa), and (IIb) according to the invention.

[0216] Preferred methods are those according to the invention, preferably as described above and / or below, wherein the reaction with hydrogen in step ii) is carried out using a catalyst, preferably a hydrogenation catalyst. This means that step ii) preferably uses or employs such a catalyst. In some cases, "hydrogenation catalyst" is also referred to as "hydrogenation catalyst," wherein, in the context of this invention, the two terms have the same definition.

[0217] Preferred methods according to the invention, preferably as described above and / or below, include steps ii) where the catalyst, preferably the hydrogenation catalyst, comprises a metal, preferably one or more metals selected from the group consisting of nickel, copper, iron, chromium, aluminum, palladium, and platinum. It is particularly preferred when the catalyst, preferably the hydrogenation catalyst, comprises a noble metal, particularly palladium (Pd) and / or platinum (Pt). In other words, a noble metal catalyst is particularly preferred.

[0218] Metals, preferably noble metals, are 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, with palladium on carbon (Pd / C) and / or platinum on carbon (Pt / C) being particularly preferred. Pt / C catalysts have been found to have the advantage of similarly achieving the conversion of mixtures of aminobenzimidazole and nitrobenzimidazole, thus enabling more complete conversion. In contrast, Pd / C catalysts are particularly preferred for reacting aminobenzimidazole, but less suitable for the corresponding nitrobenzimidazole.

[0219] The preferred method is the one according to the invention, preferably as described above and / or below, wherein the reaction with hydrogen in step ii) is carried out for a duration of 1 to 30 hours, preferably 3 to 22 hours, particularly preferably 5 to 16 hours, and especially preferably 8 to 13 hours.

[0220] The preferred method is the one according to the invention, preferably as described above and / or below, wherein the reaction with hydrogen in step ii) is carried out in a pressure reactor, preferably in an autoclave.

[0221] The method according to the invention is particularly preferred, wherein the reaction in step ii)

[0222] - Using a catalyst; and / or (preferably) and

[0223] - Performed at a temperature of 40°C to 190°C, preferably 55°C to 170°C, particularly preferably 70°C to 150°C, especially preferably 85°C to 130°C; and / or (preferably and)

[0224] - Performed at a pressure of 20 to 70 bar, preferably 28 to 57 bar, and particularly preferably 35 to 45 bar.

[0225] In the method according to the invention, the ketone in step ii) is a subsequent group R. 1 It is a ketone derivative; in the case of an aldehyde, it is accordingly an aldehyde derivative. Ketones are given particular preference, and methyl isobutyl ketone (MIBK) is the most preferred.

[0226] The preferred method according to the invention, preferably as described above and / or below, is the method in which a solvent is used in step ii), wherein the solvent is preferably the same as or different from the ketone / aldehyde (preferably the same).

[0227] If the ketone / aldehyde is the same as the solvent, then the solvent is additionally a reactant. This is preferably the case if the aldehyde / ketone is in liquid form under the reaction conditions. If the ketone / aldehyde is not in liquid form under the reaction conditions, then the solvent is preferably inert, i.e., not a reactant itself. Preferred inert solvents include toluene, dioxane (preferably 1,4-dioxane), 2-methyltetrahydrofuran (2-MTHF), and / or xylene. This is preferably the case if the aldehyde / ketone is in solid form under the reaction conditions. In the latter case, it is preferable to use only the stoichiometric amount (preferably slightly excess in some cases) of the ketone / aldehyde as a reactant.

[0228] Particularly preferred is the method according to the invention, preferably as described above and / or below, wherein the ketone / aldehyde, particularly preferably the ketone, is in liquid form in step ii), particularly preferably as a solvent and reactant. This makes it possible to eliminate the need for any additional compounds, such as toluene or xylene.

[0229] Preferred methods are those according to the invention, preferably as described above and / or below, wherein step ii) is followed by one or more purification steps, preferably filtration, chromatography, recrystallization, and / or washing with a solvent. Preferred solvents, different from those used in step ii), include alcohols and / or 2-MTHF, preferably methanol and / or ethanol, particularly preferably ethanol. Chromatography involving silica gel is preferred. Recrystallization from hydrocarbons, preferably C5 to C20 aliphatic compounds, particularly preferably cyclohexane and / or cycloheptane is preferred. Detailed Implementation

[0230] The invention will now be explained in more detail with the aid of exemplary embodiments.

[0231] Synthesis of compounds of formula (I):

[0232] Compounds having formula (III), as exemplary embodiments of compounds having formula (I), are prepared by a number of steps specified below:

[0233] Stage 1 (Synthesis of 2-phenyl-1H-benzo[d]imidazol-6-amine):

[0234] 2-Phenylacetyl-1H-benzo[d]imidazol-6-amine was prepared according to C. Diaz, J. Comput. Aided Mol Des. [Journal of Computer-Aided Molecular Design], 2015, 29, 143-154. This yielded a mixture containing an amine (80%) and the corresponding nitro compound (20%).

[0235] Stage 2 (N-(1,3-dimethylbutylamino)-2-phenyl-1H-benzo[d]imidazol-6-amine):

[0236] According to the following scheme, the mixture obtained in stage 1 is converted in stage 2 using a platinum-carbon (Pt / C) catalyst.

[0237]

[0238] 0.80 g (3.82 mmol, 0.8 equivalent) of 2-phenyl-1H-benzo[d]imidazole-6-amine, 0.20 g (0.84 mmol, 0.2 equivalent) of 6-nitro-2-phenyl-1H-benzo[d]imidazole, 0.40 g of platinum carbon (5%; 0.4 g on 4.67 mmol substrate), and 20.0 ml of methyl isobutyl ketone (MIBK) were weighed into a stainless steel autoclave lined with Teflon. The reaction mixture was then subjected to hydrogen at 40 bar and stirred at 120°C for 10 hours. After termination of the reaction, excess hydrogen was released. The resulting product was a suspension, which was filtered through diatomaceous earth and then washed with ethanol. The resulting filtrate was concentrated to dryness and then further dried under vacuum. The dried product was purified by column chromatography (dichloromethane / methanol; 100:0 => 95:5). The purified product obtained was a reddish-brown solid; the yield was 0.31 g (23% of the theoretical value).

[0239] 1H-NMR (500 MHz, DMSO-d6) δ = 12.28 (s, 1H), 8.06 (d, J = 7.8 Hz,2H), 7.49 (t, J = 7.6 Hz, 2H), 7.40 (t, J = 7.5 Hz, 1H), 7.35 – 7.30 (m, 1H), 6.56 (d, J = 10.4 Hz, 2H), 4.36 (t, 1H), 3.45 (tt, J = 6.8, 4.1 Hz, 1H), 1.78 (dh, J = 13.5, 6.8 Hz, 1H), 1.50 (dt, J = 13.8, 7.0 Hz, 1H), 1.23 (dt, J =13.7, 6.9 Hz, 1H), 1.13 (d, J = 6.2 Hz, 3H), 0.95 (d, J = 6.6 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H).

[0240] 13 C-NMR (126 MHz, DMSO-d6) δ = 148.5, 145.7, 137.0, 136.2, 131.3,129.2, 129.1, 126.0, 119.6, 111.5, 92.0, 46.5, 46.4, 25.1, 23.3, 23.0, 21.1,19.0.

[0241] Mass spectrometry results: ESI-MS [M+H] + = 294

[0242] Measurement of oxidation induction time (OIT)

[0243] Under laboratory conditions, the potential protective effects of compounds with formula (III) as aging stabilizers / antioxidants were investigated by measuring oxidation induction time.

[0244] Therefore, compounds having formula (III) and 6PPD for comparison (in each case with polymers (liquid-synthesized polyisoprene (IR), LIR-50, Kuraray, weight-average molecular weight distribution M)) were compared. w = 54,000 g / mol, glass transition temperature T g = -63°C) together) heated at 180°C until oxidation begins. In the context of this invention, this required time is the aforementioned "oxidation induction time".

[0245] Heat to 180°C:

[0246] The initial temperature was 35°C, and the temperature was initially heated to 170°C at a heating rate of 20 K / min (Kelvin / min), and then further heated to 180°C at a heating rate of 1 K / min (purge gas: nitrogen (N2), volumetric flow rate 50 ml / min).

[0247] Under N2 atmosphere, the sample was kept isothermally at 180ºC for 5 minutes, and then the atmosphere was switched to O2 atmosphere (volume flow rate 50 ml / min).

[0248] Oxidation was observed by DSC (differential scanning calorimetry). The time until the onset of oxidation was measured (in minutes) in each case. Results compared to the known aging stabilizer 6PPD are summarized in Table 1.

[0249] Table 1. Oxidation induction time in [min]

[0250]

[0251] Table 1 shows that, compared with 6PPD, the compound having formula (III) achieved a significantly improved protective effect at a temperature of 180°C, which is considered particularly harsh, because the time required for oxidative detection was unexpectedly longer. The improvement observed in this experiment was approximately 100%.

[0252] Compounds generally having formula (I) and particularly having formula (III) are based on the benzimidazole basic structure, especially the 2-phenylbenzimidazole basic structure. In contrast, 6PPD is based on the diphenylamine basic structure. Benzimazole or phenylbenzimidazole poses significantly less harm to the environment and health.

[0253] Therefore, the compounds of formula (III) according to the present invention, which are representative of compounds of formula (I) according to the present invention, are not only more environmentally friendly and less harmful to health than other representatives of this known compound class, but also achieve excellent protective effects.

[0254] As a representative of the compounds of formula (I) according to the present invention, the compounds of formula (III) according to the present invention exhibit sufficient solubility in rubber mixtures.

[0255] In supplemental tests, solubility was further improved when the phenyl ring carried an alkyl substituent or when the phenyl ring was fully hydrated (data not shown).

[0256] For use in rubber compounds for vehicle tires (particularly preferred herein), compounds of formula (I) according to the invention, represented by compounds of formula (III), are added in one of the mixing stages of the rubber compound production process in a manner known to those skilled in the art, for example, in place of aging stabilizers known in the art such as 6PPD, 7PPD, or IPPD.

[0257] For this purpose, compounds having formula (III) are incorporated, for example, in different amounts (see Table 2). The resulting examples of the invention are identified as E1 and E2.

[0258] The comparative examples are rubber mixtures of otherwise identical composition containing 6 PPD instead of compounds of formula (III) as aging stabilizers, wherein, in each case, substitutions are made between V1 and E1 and between V2 and E2 on a mole / mole basis. Amounts in Table 2 are reported in phr. The reference (ref.) does not contain aging stabilizers.

[0259] In all mixtures, the total amount of aging stabilizer (6 PPD or a compound having formula (III)) and plasticizer oil MES is 10 phr.

[0260] Table 2, Exemplary Rubber Compounds [phr]

[0261]

[0262] Examples of rubber compounds according to the invention also show at least equal or even improved aging stabilization effects compared to typical rubber compounds, especially those known from the prior art (data not shown). In contrast, the references show completely inadequate aging stabilization effects.

Claims

1. A compound having formula (I): (I)， in - R 1 Choose from the following groups: - xi) Aromatic groups and - xii) Aliphatic C3-to-C 12 - group, - R 2 and R 3 They are either the same or different and are independently selected from the following groups: Aliphatic C1-to-C 12 - Groups, aromatic groups, halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups, - m can be 0, 1, 2, or 3. - n is 0, 1, 2, 3, or 4, and - X is an aromatic or aliphatic ring.

2. The compound of claim 1, wherein, X contains 6 carbon atoms, preferably phenyl or cyclohexyl.

3. The compound according to claim 1 or 2, wherein, The compound has the structure of formula (Ia) or (Ib). (Ia), (Ib), Where R 1 R 2 R 3 m and n are as defined in claim 1.

4. The compound according to any one of claims 1 to 3, wherein, The compound has the structure of formula (IIa) or (IIb). (IIa), (IIb), Where R 1 R 2 R 3 m and n are as defined in claim 1.

5. The compound according to any one of claims 1 to 4, wherein, n and m can be the same or different.

6. The compound of claim 4 or 5, wherein, In equations (Ia) and / or (IIa), m is zero and n is 1, and preferably, R 3 It is an aliphatic C1-to-C 12 - group.

7. The compound of claim 4 or 5, wherein, In equations (Ib) and / or (IIb), m and n are zero.

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

9. The compound according to any one of claims 1 to 8, wherein, The structure having formula (III) includes: (III).

10. A rubber compound comprising the compound as described in any one of claims 1 to 9, preferably comprising one or more diene rubbers.

11. A vehicle tire, preferably a pneumatic vehicle tire, comprising, in at least one component, preferably in at least one external component, the rubber compound as described in claim 10, wherein the external component is preferably a tread, sidewall, and / or flange profile.

12. The compound according to any one of claims 1 to 9 is preferably used as an aging stabilizer and / or antioxidant in the following ways: - Vehicle tires, especially pneumatic vehicle tires; - Unlike rubber products for vehicle tires, these are particularly preferably selected from the group consisting of: air springs, bellows, belts, drive belts, hoses, profiles, seals, films, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and sole parts; - Oils and / or greases; and / or - Fuel and / or lubricant.

13. The rubber compound of claim 10 is used for the production of the following applications: - Vehicle tires, preferably pneumatic vehicle tires, and / or - Unlike rubber products for vehicle tires, these are particularly preferably selected from the group consisting of: air springs, bellows, belts, drive belts, hoses, profiles, seals, films, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and sole parts.

14. A method for producing a compound having formula (I), the method comprising the following steps: i) Producing or supplying compounds having formula (B1): (B1)， ii) React the compound having formula (B1) with the following: - Hydrogen and ketones or aldehydes, preferably ketones, To obtain the compound having formula (I): (I)， in - R 1 Choose from the following groups: - xi) Aromatic groups and - xii) Aliphatic C3-to-C 12 - group, - R 2 and R 3 They are either the same or different and are independently selected from the following groups: Aliphatic C1-to-C 12 - Groups, aromatic groups, halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups, - m can be 0, 1, 2, or 3. - n can be 0, 1, 2, 3, or 4. - X is an aromatic or aliphatic ring, and - Z is selected from the group consisting of: halogens, sulfonates, leaving groups based on sulfonates, amino and nitro groups, preferably amino and nitro groups.

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

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