Compounds, rubber blends containing the compounds, vehicle tires comprising the rubber blend as at least one component, methods for producing the compounds, and use of the compounds as anti-aging means and / or antioxidants and / or dyes.

Abstract

The present invention relates to a compound, a rubber mixture containing the compound, a vehicle tire containing the rubber mixture in at least one component, a method for producing the compound, and the use of the compound as an anti-aging stabilizer and / or antioxidant and / or dye. The compound according to the invention has the formula I): the compound of TIFF2026509248000023.tif26170, in which - R 1 is - xi) an aromatic radical, and - xii) an aliphatic C3-C 12 radical selected from the group consisting of - R 2 and R 3 are the same or different and independently an aliphatic C1-C 12 radical, an aromatic radical, a halogen radical, a cyano radical, an ester radical, a ketone radical, an ether radical, and a thioether radical selected from the group consisting of - m is 0 or 1 or 2 or 3, - n is 0 or 1 or 2 or 3 or 4, - X is selected from the group consisting of O, S and N(H), - Y is selected from the group consisting of O, S and N(H).

Description

Technical Field

[0001] The present invention relates to a compound, a rubber mixture containing the compound, a vehicle tire containing the rubber mixture in at least one component, a method for producing the compound, and the use of the compound as an anti-aging agent and / or antioxidant and / or dye.

Background Art

[0002] Polymer materials, especially rubbers, are known to be used in vehicle tires and rubber articles other than vehicle tires (preferably technical rubber articles). Not only natural rubber and synthetic polymers (such as IR, BR, SSBR, ESBR, etc.), but also natural and synthetic oils, greases, and lubricating oils are subject to oxidation reactions that adversely affect their original desired properties during long-term storage, especially in applications that are frequently used at high temperatures. Depending on the type of polymer, the polymer chains may become shorter (until the material liquefies), or the material / article may subsequently become undesirably hard. [[ID=,14]]

[0003] Therefore, anti-aging agents overwhelmingly contribute to improving the durability of vehicle tires / rubber articles.

[0004] Typical anti-aging agents include 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, especially anti-aging agents in general, can react with oxygen, ozone, and / or free radicals, preferably alkyl radicals, alkoxy radicals, and alkylperoxy radicals, to capture them, thereby protecting the polymer, especially from undesirable oxidation and free radical reactions. Anti-aging agents that react with ozone to capture ozone are often also called "anti-ozone degradation agents".

[0005] However, the drawback of the aforementioned compounds is that they are suspected of being potentially carcinogenic.

[0006] A further challenge associated with anti-aging stabilizers is undesirable blooming. Here, because the molecules of anti-aging stabilizers have relatively low solubility in the polymer matrix surrounding the tire / rubber article, they diffuse to the surface of the article, often forming a film there that is normally distinguishable from the rest of the article by its color. In the case of vehicle tires, this typically manifests as brown discoloration of the otherwise black sidewalls. In addition to the aesthetic drawback, this also relates to a drawback in terms of anti-aging stabilization effectiveness. This is because the compounds that have come to the surface due to blooming are removed or leached out of the vehicle tire by this process. This first reduces the total amount of anti-aging stabilizer, and along with the effect of further diffusion of anti-aging stabilizer molecules toward the surface, resulting in a continued decrease in the level of protection, which often occurs. [Overview of the project] [Problems that the invention aims to solve]

[0007] The object of the present invention is to provide novel compounds that can be used as aging stabilizers, particularly in vehicle tires and / or other rubber articles different from vehicle tires, preferably industrial rubber articles, and moreover, novel compounds that have sufficient solubility in their respective matrices, such as polymers, and have lower potential hazards. This is intended to ensure continuous and optimal protection from oxygen, free radicals, and / or (preferably and) ozone, minimizing and even preventing the tendency to bloom while reducing health hazards.

[0008] The compound is also intended to ensure aging stabilization that is equivalent to or even better than that of known aromatic amines such as 6PPD. [Means for solving the problem]

[0009] This problem is represented by equation (I): [ka] (In the formula, - R 1 teeth, - xi) Aromatic radicals, and - xii) Aliphatic C3~C 12 radical Selected from the group consisting of, - R 2 and R 3 They are either the same or different, and independently, Aliphatic C1~C 12 Selected from the group consisting of radicals, aromatic radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals, - m is 0, 1, 2, or 3, - n is 0, 1, 2, 3, or 4, - X is selected from the group consisting of O, S, and N(H), - Y is selected from the group consisting of O, S, and N(H). This is resolved by compounds that conform to the formula.

[0010] The compound of formula (I) according to the present invention is a dibenzodiazepinone derivative and exhibits lower potential hazards compared to known aging stabilizers based on aniline and its degradation products. This is an obvious advantage in vehicle tires and rubber articles other than vehicle tires (preferably industrial rubber articles), where rubber components are often released by wear / other degradation processes. The basic structure of dibenzodiazepinone compounds is also used in many orally administered drugs.

[0011] The compound of formula (I) according to the present invention exhibits, in fact, particularly in rubber mixtures / vehicle tires, an improved aging stabilization effect over a wide temperature range compared to the known conventional aging stabilizer 6PPD (see the examples below).

[0012] The compounds of formula (I) according to the invention are preferably anti-ozone degradation agents, and particularly preferably are also anti-ozone degradation agents. That is, in addition to being capable of reacting with oxygen and / or free radicals (preferably as described above), they are also anti-ozone degradation agents.

[0013] The compounds of formula (I) according to the invention are preferably suitable as alternatives to 6PPD, the decomposition products of which are particularly extremely toxic to Oncorhynchus gorbuscha and thus probably also to other aquatic organisms.

[0014] In the context of the present invention, O and S in the groups X and Y in formula (I) are defined as follows: O represents oxygen and S represents sulfur. This also applies to the preferred compounds according to the invention.

[0015] When m or n is 0 (zero), the radical R 2 or R 3 does not exist and they are replaced by hydrogen atoms instead. This preferably applies independently. R 2 and R 3 are preferably optional in the compounds according to the invention.

[0016] Similarly, the expression of the bonds of (R 2 ) m , (R 3 ) n and NHR 1 to the benzene ring of the structure is, of course, excepted from being arranged two or more at the same position, as already excluded by the tetravalent nature of the carbon atoms of the benzene ring. It is obvious to those skilled in the art that this means that these groups are arranged at any position in the benzene ring assigned in each case. In the context of the present invention, the radical NHR 1 is the same as N(H)R 1 . That is, regarding secondary amines.

[0017] In the context of the present invention, "C3-C 12The term "radical" is understood to mean a radical containing 3 to 12 carbon atoms. This is also true for similar names such as "C1-C12 radicals." Independently, "C1" is used to represent the highest oxidation state or the highest priority carbon atom position under the Kahn-Ingold-Prelude rule (CIP). The meanings of each will be obvious to those skilled in the art.

[0018] With respect to the present invention, the present invention should not be bound in general by a particular mechanism of action or a particular explanation.

[0019] Furthermore, the compound of formula (I) according to the present invention has sufficient, even excellent, solubility for rubber mixtures, particularly for vehicle tires and rubber articles other than vehicle tires (particularly industrial rubber articles). This minimizes, and even virtually prevents, undesirable blooming of the compound, which is advantageous for its aging stabilization effect. The less blooming of the aging stabilizer, the less of the aging stabilizer is lost from the surface, intentionally or unintentionally, resulting in less subsequent diffusion of the aging stabilizer. [Modes for carrying out the invention]

[0020] The present invention encompasses all preferred embodiments, particularly those reflected in the claims. The present invention also includes and discloses embodiments arising from combinations of different features (each with a different level of priority), and therefore, combinations of a first feature described as “preferred” and a second feature described as, for example, “particularly preferred” are also included in the present invention.

[0021] Furthermore, all information relating to the characteristics of the compounds of the present invention also applies to the method of the present invention for producing the compounds, the rubber mixtures of the present invention containing the compounds, and the uses of the present invention.

[0022] Compound of formula (I): NHR 1Compounds of formula (I) in which the element is positioned meta relative to X are preferred. Therefore, compounds of formula (I) having the structure of formula (II) are particularly preferred: [ka] (In the formula, R 1 , R 2 , R 3 (where X and Y, and m and n are as defined above, preferably as defined above as preferred).

[0023] The descriptions made in this text in relation to the compound of formula (I) are, in particular, also applicable mutatis mutandis to the compound of formula (II).

[0024] The compound of formula (II) particularly readily achieves the objectives of the present invention and exhibits sufficient, and even excellent, solubility, especially in rubber mixtures for vehicle tires.

[0025] In the compounds of formulas (I) and (II), X is selected from the group consisting of O, S, and N(H), and X is incorporated into the ring structure. When X is N(H), it will be apparent to those skilled in the art that the nitrogen atom (N) is bonded to the adjacent carbon atom in the ring structure, and the hydrogen atom (H) is bonded only to the nitrogen atom.

[0026] Compounds of formula (I) and / or (II) where X is N(H) are particularly preferred. This is particularly good at achieving the objectives of the present invention and, in particular, provides excellent aging stability by protection from oxidation in polymer and / or rubber mixtures, especially polymer and / or rubber mixtures for vehicle tires.

[0027] In the compounds of the present invention of formulas (I) and (II), Y is terminally bonded to a carbon atom of the central ring assigned according to the formula and is selected from the group consisting of O, S, and N(H). When Y is N(H), it will be apparent to those skilled in the art that the nitrogen atom (N) is bonded to an adjacent ring carbon atom via a double bond, and the hydrogen atom (H) is bonded only to the nitrogen atom.

[0028] Compounds of the present invention of formula (I) and / or (II), where Y is O, are particularly preferred. This is particularly good at achieving the objectives of the present invention and, in particular, provides excellent protection from oxidation in polymers and / or rubber mixtures, especially polymers and / or rubber mixtures for vehicle tires.

[0029] Compounds of the present invention of formula (I) and / or (II) are particularly preferred, where X is N(H) and / or Y is O, preferably X is N(H) and Y is O.

[0030] In the compounds of the present invention of formula (I) and / or (II), radical R 2 and R 3 They are either identical or different, and independently, aliphatic C1-C 12 Selected from the group consisting of radicals, aromatic radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals.

[0031] R 2 and R 3 The aliphatic C1-C inside 12 Compounds according to the present invention of formula (I) and / or (II) are preferred, wherein the radicals independently include linear partial radicals, branched partial radicals, and / or cyclic partial radicals; preferably linear, branched, or cyclic.

[0032] R 2 and R 3 The aliphatic C1-C inside 12 Compounds according to the present invention of formula (I) and / or (II) are preferred, wherein the radicals are independently saturated or unsaturated, preferably saturated.

[0033] R 2 and R 3 The aliphatic radicals inside are aliphatic C1-C 10Compounds according to the present invention of formula (I) and / or (II) are preferred, which are radicals, preferably aliphatic C1-C8 radicals, more preferably aliphatic C1-C6 radicals, particularly preferably aliphatic C1-C4 radicals, very preferably aliphatic C1-C2 radicals, preferably methyl and / or ethyl.

[0034] In some cases, R 2 and R 3 The aliphatic C1-C inside 12 Compounds of formula (I) and / or (II) according to the present invention are preferred, wherein the radical independently represents one or more halogen substituents selected from the group consisting preferably of fluorine, chlorine, and bromine.

[0035] R 2 and R 3 Compounds according to the present invention of formula (I) and / or (II) are preferred, wherein the aromatic radicals within the compound independently contain 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.

[0036] R 2 and R 3 Compounds of formula (I) and / or (II) according to the present invention are preferred, wherein the aromatic radical in the compound independently represents one or more halogen substituents selected from the group consisting preferably of fluorine, chlorine, and bromine.

[0037] R 2 and R 3 Compounds of formula (I) and / or (II) according to the present invention are preferred, wherein the halogen radical in the compound is independently selected from the group consisting of fluorine, chlorine, and bromine.

[0038] R 2 and R 3Compounds according to the present invention of formula (I) and / or (II) are preferred, wherein the ester radical, ketone radical, ether radical, and thioether radical in the compound independently contain 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 7 carbon atoms, and most preferably 1 to 5 carbon atoms. In some cases, it is preferable to combine the aforementioned upper limit of carbon atoms with a lower limit of at least 2 carbon atoms.

[0039] Listed radicals R 2 and R 3 Particularly preferably, these may already be bonded to their respective benzene rings / precursors by the selection of an appropriate starting compound.

[0040] Compounds of the present invention of formula (I) and / or (II) are more preferable, where m is zero (0) and / or n is zero (0), preferably m is zero (0) and n is zero (0).

[0041] Compounds according to the present invention having a structure according to formula (Ia) or (IIa) of formula (I) and / or (II) are most preferred: [ka] (wherein X, Y, and R are shown in the formula) 1 (As defined above). X, Y, and R 1 The descriptions made herein in relation to this matter shall also apply mutatis mutandis.

[0042] Compounds of the present invention of formula (Ia) and / or (IIa) are preferred, where X is N(H) and / or Y is O, preferably X is N(H) and Y is O.

[0043] In the compounds according to the present invention, preferably compounds according to formula (I), (Ia), (II), and / or (IIa), the radical R 1 The following group is selected: - xi) Aromatic radicals, and - xii) Aliphatic C3~C 12 radical.

[0044] In some cases, compounds according to the present invention are preferred in which the aromatic radical in xi) is a substituent selected from the group consisting of halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals; particularly preferably, the compounds include ester radicals, ketone radicals, ether radicals, and thioether radicals. In other cases, particularly preferably, the aromatic radical in xi) does not have the aforementioned substituents and is preferably not substituted at all.

[0045] A compound according to the present invention is preferred in which the aromatic radical in xi) contains 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.

[0046] Compounds according to the present invention are particularly preferred in which the aromatic radical in xi) includes a phenyl radical (i.e., -C6H5) and / or a benzyl radical (i.e., -CH2-C6H5), most preferably a phenyl radical.

[0047] In some cases, R 1 It is preferable that the aromatic radicals within the molecule are not substituted with the first carbon atom or two carbon atoms adjacent to the C1 atom, i.e., carbon atoms bonded to the N atom. Therefore, for example, in the basic benzene structure, it is preferable that there are no substituents at the ortho and / or meta positions relative to the N atom.

[0048] xii) Aliphatic C3~C 12 The compounds according to the present invention are preferred in which the radical comprises a linear partial radical, a branched partial radical, and / or a cyclic partial radical; preferably linear, branched, or cyclic, and most preferably branched.

[0049] xii) Aliphatic C3~C 12Compounds according to the present invention are preferred in which the radical is saturated or unsaturated, preferably saturated.

[0050] xii) In this case, the aliphatic radical is aliphatic C3~C 10 Compounds according to the present invention that are radicals, preferably aliphatic C4-C8 radicals, and more preferably aliphatic C5-C7 radicals, are particularly preferred.

[0051] R 1 Compounds according to the present invention that contain a tertiary carbon atom bonded to a nitrogen atom (N) are preferred. The nitrogen atom (N) is preferably a secondary nitrogen atom.

[0052] In relation to the present invention, the term "tertiary carbon atom" is understood to mean a carbon atom having only one bonded hydrogen atom. Compared to secondary and quaternary carbon atoms, this provides particularly superior protective effects, preferably in rubber mixtures (particularly preferably in vehicle tires and / or other rubber articles other than vehicle tires (particularly industrial rubber articles)). Optimized reactivity is achieved with respect to mechanisms related to stabilization against aging, which avoids undesirable side reactions.

[0053] R 1 However, the compounds according to the present invention are particularly preferred, which are branched or cyclic alkyl radicals containing 3 to 12 carbon atoms in each case, preferably 3 to 8 carbon atoms in each case, and especially preferably 4 to 7 carbon atoms in each case.

[0054] R 1 Compounds according to the present invention are highly preferred, wherein the compound is 1,3-dimethylbutyl or cyclohexyl, preferably 1,3-dimethylbutyl. This provides particularly excellent solubility in rubber mixtures, especially preferably for vehicle tires and rubber articles other than vehicle tires (preferably industrial rubber articles).

[0055] Formula (III): [ka] Compounds according to the present invention having a structure that conforms to the above are particularly preferred.

[0056] The compound of formula (III) exhibits excellent solubility in polymers, particularly rubber mixtures, especially preferably rubber mixtures of vehicle tires and rubber articles other than vehicle tires (especially preferably industrial rubber articles). Furthermore, the compound of formula (III) can be produced by a relatively simple, energy-efficient, and low-cost method, and also exhibits improved protective effects compared to 6PPD (see the examples below). According to IUPAC nomenclature, the compound of formula (III) according to the present invention is: It is also called 8-(1,3-dimethylbutylamino)-5,10-dihydro-11Hdibenzo[b,e][1,4]diazepine-11-one.

[0057] Rubber mixtures containing compounds according to formula (I): The present invention further relates to a rubber mixture comprising the compounds according to the present invention described above (preferably those listed above as preferred), and preferably comprising one or more diene rubbers. The rubber mixture preferably comprises one or more compounds according to the present invention, and at least one of the rubbers is a diene rubber.

[0058] The foregoing provisions relating to the compounds of the present invention described herein as particularly preferred also preferably apply mutatis mutandis to the rubber mixtures of the present invention.

[0059] Therefore, the rubber mixture according to the present invention contains at least one type of rubber. In principle, the rubber mixture according to the present invention is any rubber mixture in which the compound according to the present invention functions as a low-toxicity aging stabilizer and / or ozone degradation inhibitor. The rubber mixture according to the present invention contains one or more types of rubber.

[0060] A rubber mixture according to the present invention comprising a compound of formula (I) or (Ia), preferably a compound of formula (II) or (IIa), and particularly preferably a compound of formula (III), is particularly preferred.

[0061] A rubber mixture according to the present invention is preferred, comprising one or more compounds of formula (I) according to the present invention, preferably only one compound of formula (I) based on the total number of dibenzodiazepinones in the rubber mixture, and particularly preferably only one compound of formula (III) based on the total number of dibenzodiazepinones in the rubber mixture. This also preferably applies to other preferred compounds according to the present invention.

[0062] A rubber mixture according to the present invention is preferred, containing a total amount of the compound of formula (I) in the form 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 preferably 1 to 3 phr. This total amount contains the compound of formula (II), and is particularly preferably containing only one compound of formula (II). This total amount is extremely preferable to contain only the compound of formula (III), preferably the compound of formula (III).

[0063] In relation to this specification, the unit "phr" (parts per 100 parts by weight of rubber) is a unit of quantity for mixing recipes common in the rubber industry. The amount of parts by weight of individual compounds used herein refers to all high molecular weight (M) compounds present in the mixture (over 20,000 g / mol). w The total mass of rubber is based on 100 parts by weight.

[0064] The rubber mixture according to the present invention preferably comprises one or more diene rubbers. Diene rubbers are typically formed by polymerization or copolymerization of dienes and / or cycloalkenes, and are therefore understood to mean rubbers having a C=C double bond in either the main chain or the side groups.

[0065] Diene rubbers include 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 molecular weight M. wA rubber mixture according to the present invention is preferred, selected from the group consisting of liquid rubber with a concentration exceeding 20,000 g / mol, butyl rubber (IIR), 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 copolymer, hydrogenated acrylonitrile butadiene rubber, and hydrogenated styrene-butadiene rubber.

[0066] In relation to the present invention, the term “natural rubber” should be understood to mean natural rubber that can be obtained from the Hevea rubber tree and from “non-Hevea” sources. Preferred non-Hevea sources are guayule shrubs and dandelions. Particularly preferred dandelions are TKS (Taraxacum Kok-saghyz; Russian dandelion).

[0067] The rubber mixture according to the present invention is particularly preferred in which 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 (XIIR).

[0068] The rubber mixture according to the present invention is highly preferable in which 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).

[0069] Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber (IIR), halobutyl rubber (XIIR), and / or ethylene-propylene-diene rubber are preferably used in the manufacture of rubber articles other than vehicle tires (but typically considered industrial rubber articles), preferably in the manufacture of straps, drive belts, hoses, belts, and / or rubber articles for shoe soles. Mixed compositions known to those skilled in the art, which are specific in terms of fillers, plasticizers, vulcanization systems, and additives, are preferably used herein.

[0070] Polyisoprene preferably includes cis-1,4-polyisoprene and / or 3,4-polyisoprene. This preferably applies whether it is natural or synthetic polyisoprene. Preferably, cis-1,4-polyisoprene having a cis-1,4 content of more than 90% by weight is preferred. Such polyisoprene can preferably be obtained by stereospecific polymerization in solution using a Ziegler-Natta catalyst or fine alkyllithium. Furthermore, natural rubber (NR) is also such cis-1,4-polyisoprene. Natural rubber (NR) containing cis-1,4-polyisoprene, and preferably having a cis-1,4 content of 99% by weight or more, is particularly preferred.

[0071] In some cases, a rubber mixture according to the present invention comprising one or more natural polyisoprenes (NR) and one or more synthetic polyisoprenes (IR) is preferred. Therefore, a polyisoprene mixture is preferred.

[0072] In some cases, the rubber mixture according to the present invention is particularly preferred, comprising one or more natural polyisoprene (NR) in a total amount preferably 56 to 130 phr, especially preferably 80 to 120 phr, very preferably 90 to 110 phr, and more preferably 95 to 100 phr. Such rubber mixtures exhibit optimized tear and abrasion properties, particularly good processability and vulcanization return 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.

[0073] In some cases, rubber mixtures according to the present invention that contain one or more types of natural polyisoprene (NR) in a total amount significantly less than 100 phr are particularly preferred. In these cases, the rubber mixture additionally contains one or more rubbers different from natural polyisoprene, preferably 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, rubber mixtures according to the present invention that contain one or more types of natural polyisoprene (NR) in a total amount of 5 to 55 phr, preferably 5 to 35 phr, more preferably 5 to 25 phr, and most preferably 5 to 20 phr are particularly preferred. Such rubber mixtures exhibit particularly good processability and vulcanization return stability, as well as optimized tear properties and optimal rolling resistance properties.

[0074] In some cases, the rubber mixture according to the present invention, which contains at least one type of butadiene rubber (BR, polybutadiene), is preferred. Butadiene rubber containing high-cis and / or low-cis types is preferred, with polybutadiene having a cis content of 90% by weight or more being called high-cis type, and polybutadiene having a cis content of less than 90% by weight being called low-cis type. A particularly preferred low-cis type is Li-BR (lithium-catalyzed butadiene rubber), which preferably has a cis content of 20% to 50% by weight. High-cis types are particularly preferred because they provide particularly excellent properties of the rubber mixture, especially low hysteresis.

[0075] In some cases, rubber mixtures according to the present invention are preferred in which butadiene rubber is functionalized at the end and / or along the polymer chain using one or more functional groups. Preferably, one or more functional groups are independently selected from the group consisting of hydroxyl groups, ethoxy groups, epoxy groups, siloxane groups, amino groups, aminosiloxane groups, carboxyl groups, phthalocyanine groups, and silane sulfide groups. However, the selection of functional groups is preferably not limited to the groups described above. In some cases, the functional groups preferably include one or more metals.

[0076] The rubber mixture according to the present invention is preferable, comprising 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, as well as optimal braking characteristics, of the rubber mixture according to the present invention.

[0077] In some cases, rubber mixtures according to the present invention comprising at least one styrene-butadiene rubber (styrene-butadiene copolymer) are preferred. Styrene-butadiene rubber comprising one or more solution-polymerized styrene-butadiene rubbers (SSBRs) and / or one or more emulsion-polymerized styrene-butadiene rubbers (ESBRs) is preferred. In relation to the present invention, the terms "styrene-butadiene rubber" and "styrene-butadiene copolymer" are used as synonyms. In some cases, rubber mixtures are preferred in which the styrene-butadiene rubber is functionalized at the end groups and / or along the polymer chain by one or more functional groups. With regard to preferred functional groups, the matters described above with respect to butadiene rubber apply mutatis mutandis.

[0078] A rubber mixture according to the present invention is preferred, comprising at least one styrene-butadiene rubber (SSBR) in a total amount of 10 to 80 phr, preferably 30 to 80 phr, and particularly preferably 50 to 70 phr. A rubber mixture according to the present invention is particularly preferred, further comprising one or more solution-polymerized styrene-butadiene rubbers (SSBRs) in an additional total amount of 10 to 80 phr, preferably 30 to 80 phr, and particularly preferably 50 to 70 phr. This achieves particularly good rolling resistance characteristics of the rubber mixture of the present invention. It is particularly preferred to use solution-polymerized styrene-butadiene rubbers (SSBRs) in combination with one or more additional rubbers. This typically achieves a balanced profile with improved properties.

[0079] In addition to one or more compounds and at least one rubber according to the present invention, the rubber mixture according to the present invention preferably includes additional components, preferably at least one filler.

[0080] The rubber mixture according to the present invention is preferable in which one or more fillers are additionally included, preferably in a total amount of 30 to 500 phr, preferably 50 to 400 phr, and more preferably 80 to 300 phr. Particularly preferred fillers are reinforcing fillers selected from the group consisting of carbon black and silicon dioxide.

[0081] Suitable carbon black generally includes all types of carbon black known to those skilled in the art. The carbon black is preferably selected from the group consisting of industrial carbon black and pyrolysis carbon black, with industrial carbon black being preferred.

[0082] It is preferable that the carbon black has an iodine value (also known as iodine adsorption) in accordance with ASTM D1510 in the range of 30-250 g / kg, preferably 35-180 g / kg, particularly preferably 40-180 g / kg, and very preferably 40-130 g / kg, and / or a DBP value in accordance with ASTM D2414 in the range of 30-200 ml / 100g, preferably 70-200 ml / 100g, and particularly preferably 90-200 ml / 100g. The DBP value in accordance with ASTM D2414 is determined using dibutyl phthalate to determine the specific absorption amount of the carbon black or light-colored filler. The use of such types of carbon black in rubber mixtures according to the present invention, particularly for vehicle tires, typically ensures an optimal balance between wear resistance and heat storage, and thus affects environmentally relevant rolling resistance. Carbon black having an iodine value in the range of 80-110 g / kg and a DBP value in the range of 100-130 ml / 100 g is particularly preferred. N339 type carbon black is extremely preferred.

[0083] In some cases, the rubber mixture according to the present invention is preferred in which carbon black is present in the rubber mixture in a total amount ranging from 0.1 to 60 phr, preferably 3 to 40 phr, particularly preferably 4 to 30 phr, and very preferably 5 to 15 phr. At these amounts, the carbon black typically exists as an auxiliary filler in combination with a main filler, preferably silicon dioxide, particularly preferably silica.

[0084] In other cases, the rubber mixture according to the present invention is preferred in which 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 particularly as the sole filler or as the main filler (more than 50% by weight based on the total amount of filler, preferably in combination with a relatively small amount of silica).

[0085] Silicon dioxide is preferably amorphous silicon dioxide and / or calcined silicon dioxide. Particularly preferred amorphous silicon dioxide includes precipitated silica (also called precipitated silicon dioxide).

[0086] 35-400m 2 / g, preferably 35-350m 2 / g, particularly preferably 85-320m 2 / g, very preferably 120-235m 2 Nitrogen surface area (BET surface area) in the range of / g (according to DIN ISO9277 and DIN66132), and / or 30-400m 2 / g, preferably 50-330m 2 / g, particularly preferably 80-300m 2 / g, very preferably 115-200m 2 Amorphous silicon dioxide having a CTAB surface area of ​​1 / g (according to ASTM D3765), preferably precipitated silica, is particularly preferred. Such silica provides particularly good physical properties of vulcanized rubber, for example, in rubber mixtures for tire treads. The advantage of processing the mixture by shortening the mixing time can also be obtained while maintaining the same product properties, resulting in improved productivity. Particularly preferred are Evonik's Ultrasil® VN3 (trade name) type silica and highly dispersible silica (so-called HD silica). A preferred highly dispersible silica is Solvay's Zeosil® 1165MP.

[0087] In some cases, the rubber mixture according to the present invention is preferred to contain at least one type of silica in a total amount preferably in the range of 30 to 500 phr, 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 (more than 50% by weight based on the total filler amount, preferably in combination with a relatively small amount of carbon black).

[0088] In some cases, the rubber mixture according to the present invention is particularly preferred, containing at least one type of silica in a total amount of preferably 5 to 100 phr, more preferably 7 to 80 phr, and most preferably 10 to 60 phr. In these amounts, the silica typically exists as an auxiliary filler, preferably in combination with a main filler, and more preferably carbon black.

[0089] A rubber mixture according to the present invention is particularly preferred, comprising at least silica and at least one type of 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 5 to 40 phr.

[0090] The rubber mixture according to the present invention preferably comprises additional fillers, i.e., fillers that are not / do not contain carbon black, silicon dioxide, or silica. These additional fillers preferably also include reinforcing fillers and / or non-reinforcing fillers.

[0091] 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.

[0092] Preferred additional reinforcing fillers include carbon nanotubes, graphite, graphene, and / or so-called "carbon silica two-phase fillers." The carbon nanotubes preferably include unmodified carbon nanotubes and / or carbon nanotubes modified with functional groups, the preferred functional groups being selected from the group consisting of hydroxyl groups, carboxyl groups, and carbonyl groups.

[0093] In relation to the present invention, the filler does not contain zinc oxide.

[0094] A rubber mixture according to the present invention containing one or more additional additives is preferred. Such additives are typically conventional additives in typical amounts, which are preferably added at least one main mixing stage during the production of the rubber mixture.

[0095] One or more additional additives may preferably include the following: a) A aging stabilizer different from both the compound of formula (I) and other compounds according to the present invention (i.e., a conventionally used aging stabilizer known in the prior art), preferably comprising paraphenylenediamine and / or dihydroquinoline, particularly preferably 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 Anti-aging stabilizers selected from the group consisting of 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ); b) An activator, preferably comprising a zinc compound (including a zinc complex) and / or a fatty acid, particularly preferably comprising zinc oxide, stearic acid, and / or zinc ethylhexanoate; c) Reagents for bonding fillers (especially for carbon black and silica), preferably comprising S-(3-aminopropyl)thiosulfate, its metal salt (especially for bonding to carbon black) and / or silane coupling agents (especially silicon dioxide, especially for bonding to silica); d) Ozone degradation inhibitor wax; e) Resin, preferably a tackifying resin; f) A compounding accelerator, preferably containing 2,2'-dibenzamide diphenyl disulfide (DBD); g) Processing aids, preferably containing fatty acid esters and / or metallic soaps, the preferred metallic soaps containing zinc soap and / or calcium soap; and / or h) A plasticizer, preferably an oil (preferably including aromatic, naphthenic and / or paraffinic mineral oils), a resin and / or a liquid polymer, particularly preferably MES (mildly extracted solvate), DAE (distilled aromatic extract), RAE (residual aromatic extract), TDAE (treated distilled aromatic extract), rubber liquefaction oil (RTL), biomass liquefaction oil (BTL) (preferably with a polycyclic aromatic content of less than 3% by weight in accordance with IP 346), triglycerides (preferably rapeseed oil), factis, hydrocarbon resins and / or a liquid polymer with an average molecular weight (measured by GPC = gel permeation chromatography in accordance with BS ISO 11344:2004) of 500 to 20,000 g / mol. When mineral oil is used, it is preferably selected from the group consisting of DAE (distillate aromatic extract), RAE (residual aromatic extract), TDAE (treated distillate aromatic extract), MES (mildly extracted solvate), and naphthenic oils.

[0096] In most cases, the following are substantially absent, preferably absent, and optionally absent: 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'-ditril-p-phenylenediamine (DTPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD), and N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD). A rubber mixture according to the present invention is particularly preferred if it does not contain 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), more preferably substantially free of paraphenylenediamine, preferably not free, optionally free of dihydroquinoline, most preferably substantially free of aging stabilizers other than the compounds of formula (I) (i.e., conventional aging stabilizers known in the prior art), preferably not free. Therefore, it is particularly preferred if the rubber mixture according to the present invention contains one or more compounds of formula (I) or (Ia), preferably formula (II) or (IIa), and particularly preferably formula (III), as the sole aging stabilizer. In relation to the present invention, "substantially free" should be understood to mean the total amount in the range of a quantitative upper limit of 0.1 phr, preferably 0 phr to 0.1 phr, and particularly preferably 0.0001 phr to 0.1 phr. An amount of zero (0), i.e., "not included," is particularly preferred. These highly preferred low amounts, including zero (0) phr, allow for equivalent protective effects with significantly reduced toxicity. The compounds according to the present invention of formula (I) or (Ia), preferably formula (II) or (IIa), and particularly preferably formula (III), are substitutes for the enumerated paraphenylenediamines known in the prior art that are typically used. In some other cases, rubber mixtures according to the present invention are preferred in which an aging stabilizer different from the compound of formula (I) (particularly paraphenylenediamine) is replaced at least partially, preferably up to 50% by weight or more, with one or more of the compounds according to the present invention. This achieves, at least partially, the advantages of the present invention, although not to the optimal degree.

[0097] As defined above, the absence of additional dihydroquinoline, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), is optional. That is, it is desirable in some cases and undesirable in others. In some cases, the rubber mixture according to the present invention is preferred, containing one or more dihydroquinolines, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), regardless of the presence or absence of paraphenylenediamine. The rubber mixture according to the present invention is preferred to contain dihydroquinoline, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), in a total amount ranging from 0.1 to 3 phr, preferably 0.5 to 1.5 phr.

[0098] Ozone degradation-preventing waxes (see d) above) are considered separately and are preferably present in the rubber mixture according to the present invention, regardless of whether or not the aging stabilizer in a) is present.

[0099] The silane coupling agent (see c) above) preferably includes any type known to those skilled in the art. The rubber mixture according to the present invention preferably comprises one or more silane coupling agents. In some cases, the rubber mixture according to the present invention preferably comprises a mixture of different silanes.

[0100] Silane coupling agents react with the surface silanol groups or other polar groups of silicon dioxide (especially silica) before being added to the rubber during rubber / rubber mixture mixing (in situ) or during pretreatment (pre-modification).

[0101] 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 further functional groups that can chemically react with the polymer's double bond (after optional dissociation). Preferred groups include -SCN, -SH, -NH2, and / or -S x-(x=2~8) is included. Silanes having an -SH group are typically also called mercaptosilanes. Preferred mercaptosilanes include preferably blocked mercaptosilanes according to International Publication No. 99 / 09036A1.

[0102] Particularly preferred silane coupling agents include 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane, 3,3'-bis(triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms (particularly preferred 3,3'-bis(triethoxysilylpropyl) tetrasulfide (TESPT) and / or its disulfide (TESPD)), and / or preferably mixtures of these sulfides having different numbers of sulfur atoms. In some cases, TESPT is preferred, particularly preferably in the form of a mixture with industrial carbon black (Evonik trade name X50S®).

[0103] Alternatively or in addition to those, preferred silane coupling agents include those described in International Publication No. 2008 / 083241A1, International Publication No. 2008 / 083242A1, International Publication No. 2008 / 083243A1, and / or International Publication No. 2008 / 083244A1. Alternatively or in addition to those, further preferred silane coupling agents include silanes sold by Momentive, USA under the name NXT (preferably 3-octanoylthio-1-propyltriethoxysilane) in various variations, and / or silanes sold by Evonik Industrie under the name VP Si363®.

[0104] The rubber mixture according to the present invention is preferable in which one or more further additives are present in a total amount ranging from 3 to 150 phr, preferably 4 to 100 phr, and particularly preferably 5 to 80 phr.

[0105] A rubber mixture according to the present invention is preferred, comprising one or more activators (see b above), preferably a zinc compound, and particularly preferably zinc oxide. Preferably, there are no restrictions on the type of zinc oxide. Granules and / or powder are preferred. The zinc oxide is preferably 100 ml. 2 Less than or equal to / g, preferably 1 to 100m 2 The BET surface area is in the range of / g. In some cases, the BET surface area is 10m 2 A zinc oxide content of less than / g is preferred. In other cases, the BET surface area is 10 to 100 m². 2 Zinc oxide in the range of / g is preferred, and so-called "nano zinc oxide" is particularly preferred.

[0106] The rubber mixture according to the present invention is preferably vulcanized afterward. This means that it is preferably used in a vulcanized state, and particularly preferably in vehicle tires or rubber articles other than vehicle tires (preferably industrial rubber articles). In relation to the present invention, the terms "vulcanized" and "crosslinked" are used as synonyms. Therefore, the rubber mixture according to the present invention is preferably a crosslinked rubber mixture. However, naturally, the rubber mixture is preferably not in a vulcanized form until the final processing.

[0107] The vulcanization of the rubber mixture according to the present invention is preferably carried out in the presence of sulfur and / or a sulfur donor, in combination with a vulcanization accelerator, wherein some of the vulcanization accelerator is preferably also a sulfur donor.

[0108] A rubber mixture according to the present invention comprising sulfur and / or one or more sulfur donors is preferred. There are no particular restrictions on the sulfur donors, and therefore, the assumed sulfur donors include, in principle, any sulfur donors known to those skilled in the art, provided that they are available in suitable form under general conditions.

[0109] A rubber mixture according to the present invention containing one or more vulcanization accelerators (in place of or in addition to a sulfur donor) is preferred.

[0110] Preferred vulcanization accelerators include thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate accelerators, and / or guanidine accelerators. Particularly preferred are one or more sulfenamide accelerators and / or one or more guanidine accelerators, and especially preferred are one or more accelerators selected from the group consisting of N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiadyl-2-sulfenmorpholide (MBS), N-tert-butyl-2-benzothiadylsulfenamide (TBBS), and diphenylguanidine (DPG).

[0111] A rubber mixture according to the present invention containing one or more vulcanization retarders is preferred. The presence of vulcanization retarders contributes, for example, to a more balanced vulcanization process.

[0112] The rubber mixture according to the present invention is preferably manufactured or supplied, and particularly preferably manufactured. This is preferably carried out by a method conventional in the rubber industry, in which a base mixture containing all components except the vulcanizing system (i.e., excluding the vulcanizing system) is prepared in one or more mixing steps, the vulcanizing system containing sulfur and compounds that affect vulcanization. That is, preferably the total amounts of sulfur, sulfur donor, vulcanization accelerator, and vulcanization retarder. By adding the vulcanizing system in the final mixing step, a finished mixture is obtained, which is preferably subjected to further processing by extrusion molding and / or calendering to obtain a desired shape. The shape thus obtained preferably determines its subsequent use, such as in vehicle tires.

[0113] The rubber mixture according to the present invention is preferred for use in the outer or inner components of vehicle tires, preferably in the outer components.

[0114] Preferably, the rubber mixture according to the present invention contains one or more strength members selected from the group consisting of fibers and cords.

[0115] The present invention further relates to a vehicle tire comprising, preferably, at least one outer component, the rubber mixture described herein as, preferably as, preferred herein, in at least one component, wherein the outer component is preferably a tread, a sidewall, and / or a flange profile.

[0116] The foregoing matters relating to the compounds and rubber mixtures according to the present invention, including preferred embodiments in each case, preferably also apply mutatis mutandis to vehicle tires according to the present invention.

[0117] The vehicle tire according to the present invention is preferably vulcanized; that is, it is not a green tire for vehicles. The vulcanized vehicle tire preferably contains a vulcanized product of at least one rubber mixture according to the present invention as a component. It is known to those skilled in the art that most compounds present, such as rubber, are already present or may be present in a chemically modified form after mixing or only after vulcanization.

[0118] The vehicle tires according to the present invention preferably include pneumatic vehicle tires and solid rubber tires.

[0119] The vehicle tire according to the present invention is preferably selected from the group consisting of industrial and construction vehicle tires, truck tires, passenger car tires, and motorcycle tires.

[0120] A vehicle tire according to the present invention is particularly preferred, which contains the rubber mixture according to the present invention as two, three, or more than three constituent components.

[0121] The present invention relates very generally and preferably to the use of the compounds of the present invention described herein, preferably as preferred herein, in rubber mixtures, preferably as aging stabilizers and / or (preferably and) antioxidants in rubber mixtures, preferably (described herein, preferably as preferred herein).

[0122] In addition, the present invention provides, preferably, the compounds according to the present invention described above as aging stabilizers and / or antioxidants (preferably as aging stabilizers), preferably - Vehicle tires, especially preferably pneumatic vehicle tires, - Rubber articles other than vehicle tires (preferably industrial rubber articles), particularly preferably selected from the group consisting of air springs, bellows, belts, straps, drive belts, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and parts of shoe soles. - Oil and / or grease, and / or - Fuel and / or lubricant Regarding use in [location].

[0123] The foregoing provisions relating to the compounds according to the present invention (including preferred embodiments) also preferably apply mutatis mutandis to the use of the present invention as aging stabilizers and / or antioxidants.

[0124] Preferred belts include conveyor belts.

[0125] In some cases, the compounds according to the present invention are preferably used as aging stabilizers and / or antioxidants in oils, greases, fuels, and / or lubricating oils, and are particularly preferred in engine-related applications.

[0126] The present invention further relates to the compounds of the present invention described herein as preferably described herein, or the rubber mixtures of the present invention described herein as preferably described herein. - Vehicle tires, particularly preferably pneumatic vehicle tires, and / or (preferably and) - Rubber articles other than vehicle tires (preferably industrial rubber articles), particularly preferably selected from the group consisting of air springs, bellows, belts, straps, drive belts, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and parts of shoe soles. This also relates to its use in manufacturing.

[0127] The foregoing provisions relating to the compounds according to the present invention (including preferred embodiments), the rubber mixtures according to the present invention, and the use of the present invention as aging stabilizers and / or antioxidants preferably also apply mutatis mutandis to the use for manufacturing according to the present invention as defined herein.

[0128] Preferred belts include conveyor belts.

[0129] The use of the rubber mixture according to the present invention is particularly preferred for manufacturing vehicle tires, particularly pneumatic vehicle tires. Use is preferably assumed for manufacturing any tire component (including outer and / or inner components), preferably for manufacturing outer components, particularly preferably for manufacturing flange profiles, treads, and / or sidewalls. Use is particularly preferred for manufacturing caps of treads having cap / base structures. The type of component is preferably determined by different molding / calendering processes during the extrusion / calendering process. Preferred inner components include squeegees, inner liners, core profiles, belts, shoulders, belt profiles, carcasses, bead reinforcements, bead profiles, and / or bandages. The rubber mixture for inner components is typically also called the body mixture. Different components having different shapes in the unvulcanized state are typically used for manufacturing green tires. The green tires, which have not yet been vulcanized, are then vulcanized.

[0130] The applications of the present invention also relate to the manufacture of rubber articles other than vehicle tires. These rubber articles preferably have a structure composed of multiple plies, and particularly preferably one or more plies include at least one strength member.

[0131] Preferred belts include rubber belts and / or conveyor belts.

[0132] The present invention further relates to the use of the compounds described above, preferably as dyes for fibers and / or polymers and / or paper and / or paints and lacquers. Particularly preferred paints and lacquers include decorative paints and decorative lacquers.

[0133] The foregoing provisions relating to the compounds according to the present invention (including preferred embodiments) also preferably apply mutatis mutandis to the use of the present invention as dyes.

[0134] The present invention further provides a method for producing a compound according to formula (I), wherein at least, i) Formula (B1): [ka] The process of manufacturing or preparing the compound; ii) The compound of formula (B1) - Hydrogen and ketones or aldehydes, preferably ketones, or - Aromatic amines, preferably aniline, Reacting with this, Equation I): [ka] (In the formula, - R 1 teeth, - xi) Aromatic radicals, and - xii) Aliphatic C3~C 12 radical Selected from the group consisting of, - R 2 and R 3They are either the same or different, and independently, Aliphatic C1~C 12 Selected from the group consisting of radicals, aromatic radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals, - m is 0, 1, 2, or 3, - n is 0, 1, 2, 3, or 4, - X is selected from the group consisting of O, S, and N(H), - Y is selected from the group consisting of O, S, and N(H), - Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, and nitro, and is preferably nitro. Steps to obtain the compound Regarding methods including

[0135] The foregoing relating to the compounds according to the present invention (preferably and especially as defined herein as preferred) also preferably apply mutatis mutandis to the manufacturing methods according to the present invention. This includes preferred embodiments, and all the above descriptions made in relation to the description of the compounds according to the present invention regarding all levels of priority and possible combinations of these features are R 1 , R 2 , R 3 This means it applies to X, Y, m, and n.

[0136] In Z, the halogen is chlorine, bromine, or iodine, and preferably chlorine. It is particularly preferable that fluorine is not present.

[0137] In Z, it is preferable that the sulfonate leaving group includes a triflate, nonaflate, mesylate, or tosylate.

[0138] A compound of formula (B1) where X is N(H), Y is O, and Z is NO2 can be produced in two or more steps, for example, according to the following scheme (S1): [ka] (In the formula, Z is a halogen, and p-TsOH represents p-toluenesulfonic acid hydrate).

[0139] In formula (I), the base N(H)R 1 Alternatively, the method according to the present invention is preferred in which, in formula (B1), group Z, preferably a nitro group, is positioned meta relative to X.

[0140] The compound of formula (I) is formula (II): [ka] The compound has the structure of formula (B1) and formula (B1a): [ka] (In the formula, R 1 , R 2 , R 3 (X, Y, and Z, as well as m and n, are as defined above, preferably as defined above.) The method according to the present invention having the following structure is particularly preferred. It is particularly preferred when X is N(H) and Y is O.

[0141] The method according to the present invention is preferable in which 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.

[0142] In step ii), the method according to the present invention is preferred in which the catalyst, preferably a 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 that the catalyst, preferably a hydrogenation catalyst, comprises a noble metal, particularly preferably palladium (Pd) and / or platinum (Pt). In other words, a noble metal catalyst is particularly preferred.

[0143] A metal, preferably a noble metal, is used on carbon (C). Particularly preferred catalysts include palladium-carbon (Pd / C), Raney nickel, and / or copper chromate, with palladium-carbon (Pd / C) being particularly preferred.

[0144] The method according to the present invention is preferable in which the reaction with hydrogen in step ii) is carried out at a temperature of 40°C to 130°C, preferably 45°C to 100°C, particularly preferably 50°C to 80°C, and most preferably 55°C to 65°C.

[0145] The method according to the present invention is preferable in which the reaction with hydrogen in step ii) is carried out at a pressure of 30 to 70 bar, preferably 35 to 45 bar, and particularly preferably 38 to 42 bar. During the reaction with hydrogen in step ii), it is preferable that the mixture is stirred for preferably 1 to 20 hours, preferably 3 to 13 hours, particularly preferably 5 to 13 hours, and particularly preferably 8 to 12 hours.

[0146] The method according to the present invention is preferable in which the reaction with hydrogen in step ii) is carried out in a pressurized reactor, preferably in an autoclave.

[0147] The reaction in step ii), preferably the reaction of hydrogen with a ketone or aldehyde, - Performed using a catalyst, and / or (preferably and) - The process is carried out at a temperature of 40°C to 130°C, preferably 45°C to 100°C, particularly preferably 50°C to 80°C, and / or (preferably and) - This is done at a pressure of 30-70 bar, preferably 35-45 bar, and particularly preferably 38-42 bar. The method according to the present invention is particularly preferred.

[0148] In the method according to the present invention, the ketone in step ii) subsequently becomes the radical R 1 It is a ketone derivative, and therefore, in the case of an aldehyde, it is an aldehyde derivative. Ketones, most preferably methyl isobutyl ketone (MIBK), are particularly preferred.

[0149] The method according to the present invention is preferable in which the solvent used in step ii) is preferably the same as the ketone / aldehyde, or different from (preferably the same as) the ketone / aldehyde.

[0150] If the ketone / aldehyde is the same as the solvent, the solvent also becomes a reactant. This is preferably the case when the aldehyde / ketone is in liquid form under the reaction conditions. If the ketone / aldehyde is different from the solvent, the solvent is preferably inert; that is, it is 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 when the aldehyde / ketone is in solid form under the reaction conditions. In the latter case, the ketone / aldehyde is used only as a reactant in the amount stoichiometrically required.

[0151] The method according to the present invention is particularly preferred in which a ketone / aldehyde, particularly preferably a ketone, is in liquid form in step ii) and particularly preferably present as a solvent and reactant. This makes it possible to omit any additional compounds such as toluene or xylene.

[0152] The method according to the present invention is preferable, which follows step ii) by one or more purifications, preferably by filtration, chromatography, recrystallization, and / or washing with a solvent. Preferred solvents, preferably different from those used in step ii), include alcohols and / or 2-MTHF, preferably methanol and / or ethanol, and particularly preferably ethanol. Chromatography with silica gel is preferred. Recrystallization from hydrocarbons, preferably C5-C20 aliphatic compounds, particularly preferably cyclohexane and / or cycloheptane is preferred.

[0153] Here, the present invention will be described more specifically with respect to exemplary embodiments. [Examples]

[0154] Synthesis of the compound of formula (I): Compound (III), as an exemplary embodiment of compound (I), was prepared by the following steps:

[0155] Step 1 (Synthesis of methyl-2-((2-amino-4-nitrophenyl)amino)benzoate): [ka] Under a protective gas atmosphere, 3.51 g (22.9 mmol, 1 equivalent) of 4-nitro-o-phenylenediamine was dissolved in 60 mL of dry o-dichlorobenzene, and 3.16 g (22.9 mmol, 1 equivalent) of potassium phosphate, 1.46 g (22.9 mmol, 1 equivalent) of copper powder, and 3.36 mL (22.9 mmol, 1 equivalent) of 2-iodobenzoate were added in sequence. The mixture was stirred at 135°C for a further 20 hours. After the reaction mixture was allowed to return to room temperature, the mixture was diluted with 100 mL of ethyl acetate, and the solid was filtered through Celite. The clear filtrate was washed with water and saturated sodium chloride solution, and then dried over sodium sulfate. The solvent was removed under vacuum, and the substance was used in the next step. Brown solid; yield 6.2 g (94% of the theoretical value). 1 H-NMR (Nuclear Magnetic Resonance) (500MHz,DMSO-d6)δ=9.03(s,1H),7.95(dd,J=8.0,1.6Hz,1H),7.67(d,J=2.6Hz,1H),7.48(dd,J =8.8,2.3Hz,2H),7.29(d,J=8.7Hz,1H),7.18(d,J=8.3Hz,1H),6.94(t,J=7.5Hz,1H),5.57(s,2H),3.86(s,3H). ESI-MS[M+H] + =288.

[0156] Second step (synthesis of 8-nitro-5,10-dihydro-11H-dibenzo[b,e][1,4]diazepine-11-one): [ka] Under a protective gas atmosphere, 120 mL of dry toluene was first placed in a flask equipped with a water separator, and 1.70 g (5.92 mmol, 1 equivalent) of methyl 2-((2-amino-4-nitrophenyl)amino)benzoate and 2.23 g (11.8 mmol, 2 equivalents) of p-toluenesulfonic acid hydrate were added. The resulting mixture was stirred overnight under reflux, and after cooling, the formed solid was filtered off. The latter was washed with saturated NaHCO3 aqueous solution, and then washed with water. After drying, a dark red solid was obtained; yield 1.2 g (72% of the theoretical value). 1 H-NMR(500MHz,DMSO-d6)δ=10.11(s,1H),8.73(s,1H),7.85(dd,J=6.1,3.0Hz,2H),7.75(d,J=7.9Hz, 1H),7.40(td,J=7.8,1.6Hz,1H),7.12(d,J=9.3Hz,1H),7.01(d,J=8.1Hz,1H),6.95(t,J=7.5Hz,1H). ESI-MS[M+H] + =256.

[0157] Third step (synthesis of 8-(1,3-dimethylbutylamino)-5,10-dihydro-11H-dibenzo[b,e][1,4]diazepine-11-one) [ka] 0.30 g (1.12 mmol, 1 equivalent (eq)) of 8-nitro-5,10-dihydro-11H-dibenzo[b,e][1,4]diazepin-11-one, 0.10 g of platinum on carbon (Pt / C) (5%) (on 0.4 g, 4.67 mmol of substrate), and 20.0 ml of methyl isobutyl ketone (MIBK) were weighed into a stainless steel autoclave fitted with a Teflon liner. The reaction mixture was then subjected to 40 bar of hydrogen (H2), and the mixture was stirred at 60 °C for 10 h. After the reaction was complete, the excess hydrogen was released, and the suspension was filtered through Celite® and washed with ethanol. The filtrate was concentrated until dry and then further dried under reduced pressure. The product was purified by column chromatography (cyclohexane / ethyl acetate). Brown solid; yield 0.18 g (50% of theory). 1 1H-NMR (500 MHz, DMSO-d6) δ = 9.68 (s, 1H), 7.68 (dd, J = 7.9, 1.7 Hz, 1H), 7.35 (s, 1H), 7.32 - 7.23 (m, 1H), 6.95 (d, J = 8.1 Hz, 1H), 6.83 (t, J = 7.6 Hz, 1H), 6.76 (d, J = 8.5 Hz, 1H), 6.27 (d, J = 2.5 Hz, 1H), 6.22 (dd, J = 8.5, 2.5 Hz, 1H), 4.95 (s, 1H), 3.32 (q, J = 6.6 Hz, 1H), 1.69 (hept, J = 6.8 Hz, 1H), 1.41 (dt, J = 13.9, 7.1 Hz, 1H), 1.16 (dt, J = 13.6, 6.9 Hz, 1H), 1.04 (d, J = 6.2 Hz, 3H), 0.89 (d, J = 6.7 Hz, 3H), 0.84 (d, J = 6.6 Hz, 3H). 13 13C-NMR (126 MHz, DMSO-d6) δ = 168.9, 152.3, 145.3, 133.2, 132.5, 131.2, 129.3, 123.2, 121.0, 120.4, 119.1, 109.3, 105.4, 46.4, 46.3, 25.0, 23.2, 23.0, 21.1. ESI-MS [M + H] + = 310.

[0158] Measurement of the oxidation induction time (OIT) The compound of formula (III) was investigated under laboratory conditions for its potential protective effect as an anti-aging stabilizer / antioxidant by measuring the oxidation induction time.

[0159] For this purpose, the compound of formula (III) and 6PPD for comparison were used, in both cases, as polymers (liquid synthetic polyisoprene (IR), LIR-50, Kuraray, weight-average molecular weight distribution M w = 54000 g / mol, glass transition temperature T g Along with -63°C, the sample was heated at three different constant temperatures (180°C; 165°C; 150°C) until oxidation began. The time required for this is the "oxidation induction time" mentioned above in this invention.

[0160] Heating to 180℃: The starting temperature is 35°C, and the system is first heated to 170°C at a heating rate of 20 K / min (Kelvin / min), then further heated to 180°C at a heating rate of 1 K / min (purge gas: nitrogen (N2), volume flow rate 50 ml / min).

[0161] The test specimen was held under an N2 atmosphere at an isothermal temperature of 180°C for 5 minutes, and then the atmosphere was switched to an O2 atmosphere (volume flow rate 50 ml / min).

[0162] Heating to 165℃: Heating to 165°C was similarly performed by first heating to 155°C at a heating rate of 20 K / min (Kelvin / min), and then heating to 165°C at a heating rate of 1 K / min.

[0163] Heating to 150℃: Heating to 150°C was similarly performed by first heating to 140°C at a heating rate of 20 K / min (Kelvin / min), and then heating to 150°C at a heating rate of 1 K / min.

[0164] Oxidation was observed using DSC (Differential Scanning Calorimetry). The time (in minutes) until the onset of oxidation was measured for each case. The results, compared with the known aging stabilizer 6PPD, are summarized in Table 1.

[0165] [Table 1]

[0166] Table 1 shows that, starting at temperatures of 150°C, the compound of formula (III) achieves a significantly improved protective effect compared to 6PPD, as the time required for oxidation to become detectable is considerably longer.

[0167] In particular, at a very suitable temperature of 150°C, there is a significant difference in the oxidative protective effect between known 6PPD and the compound of formula (III), with the difference exceeding 50%.

[0168] Therefore, the compound according to the present invention of formula (III), as a representative example of the compound according to the present invention of formula (I), not only has a lower environmental impact than 6PPD / another representative example of this known classification of substances, but also causes less harm to health. Furthermore, the compound / classification of compounds according to the present invention also achieves a much better protective effect.

[0169] As a representative example of the compound according to the present invention of formula (I), the compound according to the present invention of formula (III) also exhibits excellent solubility in rubber mixtures. This minimizes so-called blooming and, consequently, has a favorable effect on the protective effect.

[0170] The compound of formula (III) is also dark brown in color and is suitable as a dye (especially for paints and lacquers), and also provides desirable additional protection against oxidative damage caused by sunlight, for example.

[0171] With regard to use (as particularly preferred herein) in rubber mixtures for vehicle tires, the compounds of the present invention of formula (I), represented by the compound of formula (III), are added in a manner known to those skilled in the art during one of the mixing stages in the manufacture of the rubber mixture, for example, in place of aging stabilizers known in the prior art (e.g., 6PPD, 7PPD, or IPPD).

[0172] For this purpose, the compound of formula (III) is formulated in various amounts, for example (see Table 2). The resulting examples of the present invention are denoted as E1 and E2.

[0173] The comparative example is a rubber mixture that contains 6PPD instead of the compound of formula (III) as an anti-aging stabilizer, but the rest of the composition is the same, and in both cases substitutions are made on a molar basis between V1 and E1 and between V2 and E2. The amounts in Table 2 are reported in phr units. A reference (Ref.) without an anti-aging stabilizer is also reported.

[0174] In all mixtures, the total amount of aging stabilizer (6PPD or compound of formula (III)) and plasticizer oil MES is 10 phr.

[0175] [Table 2]

[0176] Examples of the rubber mixture according to the present invention demonstrate at least equivalent, and even improved, aging stabilization effects compared to typical rubber mixtures, particularly those known from the prior art (data not shown). References clearly show insufficient aging stabilization effects.

Claims

1. Compound of formula (I): 【Chemistry 1】 (In the formula, - R １ teeth, - xi) Aromatic radicals, and - xii) Aliphatic C ３ ~C １２ radical Selected from the group consisting of, - R ２ and R ３ They are either the same or different, and independently, aliphatic C １ ~C １２ Selected from the group consisting of radicals, aromatic radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals, - m is 0, 1, 2, or 3. - n is 0, 1, 2, 3, or 4, - X is selected from the group consisting of O, S, and N(H), - Y is selected from the group consisting of O, S, and N(H).

2. Formula II): 【Chemistry 2】 having the structure, wherein R １ , R ２ , R ３ , X, and Y, and m and n are as defined in claim 1, a compound according to claim 1.

3. The compound according to claim 1 or 2, characterized in that X is N(H) and / or Y is O, preferably X is N(H) and Y is O.

4. The compound according to any one of claims 1 to 3, characterized in that m is zero (0) and / or n is zero (0), preferably m is zero (0) and n is zero (0).

5. R １ The compound according to any one of claims 1 to 4, characterized in that it contains a tertiary carbon atom bonded to a nitrogen atom (N).

6. R １ The compound according to any one of claims 1 to 5, characterized in that it is 1,3-dimethylbutyl or cyclohexyl, preferably 1,3-dimethylbutyl.

7. Formula (III): 【Transformation 3】 A compound according to any one of claims 1 to 6, characterized by having the structure described above.

8. A rubber mixture containing the compound described in any one of claims 1 to 7, preferably containing one or more diene rubbers.

9. A vehicle tire comprising the rubber mixture according to claim 8 in at least one component, preferably at least one outer component, wherein the outer component is preferably a tread, sidewall and / or flange profile.

10. A compound according to any one of claims 1 to 7, preferably as an anti-aging stabilizer and / or antioxidant. - Vehicle tires, especially preferably pneumatic vehicle tires, - Rubber articles other than vehicle tires, particularly preferably selected from the group consisting of air springs, bellows, belts, straps, drive belts, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and parts of shoe soles, - Oil and / or grease, and / or - Fuel and / or lubricant Use in [location].

11. A compound according to any one of claims 1 to 7 or a rubber mixture according to claim 8, - Vehicle tires, especially preferably pneumatic vehicle tires, - Rubber articles other than vehicle tires, particularly preferably selected from the group consisting of air springs, bellows, belts, straps, drive belts, hoses, profiles, seals, membranes, tactile sensors for medical applications, tactile sensors for robotic applications, shoe soles and parts of shoe soles, For use in manufacturing.

12. Use of any one of the compounds described in claims 1 to 7, preferably as dyes for fibers and / or polymers and / or paper and / or paints and lacquers.

13. A method for producing a compound of formula (I), wherein at least, i) Formula (B1): 【Chemistry 4】 A process of manufacturing or preparing a compound; ii) The compound of formula (B1) above, - Hydrogen and ketones or aldehydes, preferably ketones, - Aromatic amines, preferably aniline, Reacting with the above equation I): 【Transformation 5】 (In the formula, - R １ teeth, - xi) Aromatic radicals, and - xii) Aliphatic C ３ ~C １２ radical Selected from the group consisting of, - R ２ and R ３ They are either the same or different, and independently, aliphatic C １ ~C １２ Selected from the group consisting of radicals, aromatic radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals, - m is 0, 1, 2, or 3. - n is 0, 1, 2, 3, or 4, - X is selected from the group consisting of O, S, and N(H), - Y is selected from the group consisting of O, S, and N(H), (Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, and nitro, and is preferably nitro.) Steps to obtain the compound A method that includes this.

14. The reaction in step ii), preferably the reaction between hydrogen and a ketone or aldehyde, - Performed using a catalyst, and / or - The process is carried out at a temperature of 40°C to 130°C, preferably 45°C to 100°C, particularly preferably 50°C to 80°C, and / or - This is carried out at a pressure of 30 to 70 bar, preferably 35 to 45 bar, and particularly preferably 38 to 42 bar. The method according to claim 13.

15. The compound of formula (I) is of formula (II): 【Transformation 6】 The compound has the structure of formula (B1), and the compound of formula (B1a): 【Transformation 7】 (In the formula, R １ , R ２ , R ３ (X, Y, and Z, as well as m and n, are as defined in claim 13.) The method according to claim 13 or 14, characterized by having the structure of [the specified structure].

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