Compounds for use as antioxidants in rubber blends, and for use in vehicle tires.

Abstract

The present invention relates to a compound of formula (I). TIFF2026517971000020.tif22170 (as defined in more detail herein) relates to a rubber blend containing the compound, a vehicle tire comprising the rubber blend in at least one component, a process for preparing the compound, and the use of the compound as an anti-aging and / or antioxidant.

Description

[Technical Field]

[0001] The present invention relates to a compound of formula (I). [ka] The present invention relates to rubber mixtures containing the compound (as further defined herein), vehicle tires comprising a rubber mixture in at least one component, methods for producing the compound, and the use of the compound as an aging stabilizer and / or antioxidant. [Background technology]

[0002] Polymer compounds, particularly rubber, are known to be used in vehicle tires and rubber articles other than vehicle tires (preferably technical rubber articles). Natural rubber (NR) and synthetic polymers (e.g., IR, BR, SSBR, ESBR, etc.), as well as natural and synthetic oils, greases, lubricants, and fuels, undergo oxidation reactions that adversely affect their original desired properties during long-term storage and in applications where they are frequently used at high temperatures. Depending on the type of polymer / long-chain compound, they may become shorter (until the article liquefies), or the material / article may subsequently harden undesirably.

[0003] Therefore, aging stabilizers overwhelmingly contribute to improving the durability of vehicle tires / rubber articles and corresponding compositions.

[0004] Typical aging stabilizers 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, and aging stabilizers in general, react with and capture oxygen, ozone, and / or free radicals, preferably alkyl radicals, alkoxy radicals, and alkylperoxy radicals, thereby protecting polymers / long-chain compounds from particularly undesirable oxidation and free radical reactions. Aging stabilizers that react with and capture ozone are often also called "ozone degradation inhibitors."

[0005] However, the drawback of the aforementioned compounds is that there is suspicion that they may be carcinogenic and / or harmful to the environment.

[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, the level of protection continues to decrease.

[0007] Anti-aging stabilizers in rubber compositions are well known. For example, U.S. Patent No. 5,140,055A discloses imidazole and benzimidazole derivatives in rubber mixtures. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] 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.

[0009] The compound is also intended to ensure aging stabilization that is at least equivalent to, or even better than, known aromatic amines such as 6PPD. [Means for solving the problem]

[0010] This problem concerns the compound according to the present invention of formula (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, - This is resolved by (X being an aromatic or aliphatic ring).

[0011] The compounds of formula (I) according to the invention are benzimidazole derivatives and exhibit a low potential risk compared to known anti-aging stabilizers based on aniline and its decomposition products. This is a clear advantage in vehicle tires and rubber articles different from vehicle tires (preferably industrial rubber articles), since the rubber components are often released by abrasion / other decomposition processes.

[0012] The compounds of formula (I) according to the invention actually show a significantly improved anti-aging stabilization (see the following examples), especially in rubber mixtures / vehicle tires, compared in particular to the known commonly used anti-aging stabilizer 6PPD.

[0013] The compounds of formula (I) according to the invention are preferably anti-ozone agents and particularly preferably also anti-ozone agents. That is, in addition to being able to react with oxygen and / or free radicals (preferably as described above), they are also anti-ozone agents.

[0014] The compounds of formula (I) according to the invention are preferably suitable as an alternative to 6PPD, the decomposition products of which are particularly extremely toxic to Oncorhynchus gorbuscha and thus probably also to other aquatic organisms.

[0015] The indices m and n represent the number of the corresponding groups R 2 and R 3 If m or n is 0 (zero), the radicals R 2 or R 3 do not exist and they are replaced by hydrogen atoms instead. This preferably applies independently. Since X is typically a ring containing at least some carbon atoms, R 3 should be regarded as a substituent on that ring and may be absent altogether (n equals zero and is replaced by hydrogen instead), single (n equals 1) or plural (n equals 2 - 4) (similarly for R 2 in the benzimidazole basic structure). R 2 and R 3Preferably, this is optional in the compounds according to the present invention.

[0016] (R) 2 ) m and NHR 1 The combination and (R 3 ) n It will also be apparent to those skilled in the art that the expression of the bond should be understood as representing a bond to any possible carbon atom in ring X. These groups are located at any position on the respective ring to which they are assigned, except, of course, two or more at the same position at the same time. In connection with the present invention, radical NHR 1 N(H)R 1 It is the same as, in other words, it relates to secondary amines.

[0017] In relation to the present invention, "C3~C 12 The term "radical" is understood to mean a radical containing 3 to 12 carbon atoms.

[0018] In relation to the present invention, the present invention should not be bound in general by any particular mechanism of action or particular description.

[0019] The compound of formula (I) according to the present invention has sufficient, and even very good, solubility for rubber mixtures, particularly for vehicle tires and rubber articles other than vehicle tires (particularly industrial rubber articles). The solubility is preferably due to the radical R 2 and / or R 3 Further optimization is achieved through the appropriate selection of the compound. This minimizes, and even virtually prevents, undesirable blooming of the compound, which in turn benefits its aging stabilization effect. Less blooming of the aging stabilizer means less of the aging stabilizer is lost from the surface, intentionally or unintentionally, resulting in less subsequent diffusion of the aging stabilizer. This also brings significant environmental benefits. [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 encompassed and disclosed in the present invention.

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

[0022] Compound according to the present invention: A compound according to the present invention, wherein the compound has the structure of formula (II): [ka] (In the formula, R 1 , R 2 , R 3 Compounds having (where m, n, and X are as defined above, and preferably as preferred herein) are preferred.

[0023] Group X is a ring or ring structure incorporated into the overall structure. When n is zero, in this case substituent R 3 Since represents hydrogen, X is monovalent. X is at least divalent when n is 1 or greater. In this case, R 3 It is at least single-bonded to ring X.

[0024] Group X is either aromatic (i.e., its carbon atoms are entirely aromatic / aromatic) or aliphatic (i.e., entirely aliphatic carbon atoms / aliphatic carbon atoms). However, in either case, it is necessarily a ring structure.

[0025] A compound according to the present invention of formula (I), preferably as described above and / or below as preferred, is preferred, wherein X comprises six carbon atoms, preferably a phenyl radical or a cyclohexyl radical.

[0026] The foregoing relating to the compound of formula (I) also, preferably with necessary modifications, relating to the compound of formula (II) and vice versa. The compound of formula (II) particularly readily achieves the objectives of the present invention and exhibits sufficient, even excellent, solubility, especially in rubber mixtures for vehicle tires.

[0027] A compound according to the present invention, wherein the compound has a structure of formula (Ia) or (Ib). [ka] (In the formula, R 1 , R 2 , R 3 Compounds having m and n as defined above, preferably as preferred herein, are particularly preferred.

[0028] In the compound of formula (Ia), X is aromatic (i.e., completely aromatic), but in the compound of formula (Ib), X is aliphatic (i.e., completely aliphatic).

[0029] Preferably, a compound according to the present invention as described above and / or below as preferred, wherein the compound has a structure of formula (IIa) or (IIb). [ka] (In the formula, R 1 , R 2 , R 3 Compounds having m and n as defined above, preferably as preferred herein, are more preferable.

[0030] In relation to the present invention, it is a fact that, in general, n are independent of each other. This means, for example, that n in formula (Ia) / (IIa) is independent of n in formula (Ib) / (IIb). This applies equally to m and all embodiments of the compounds according to the present invention.

[0031] In connection with the present invention, R 2 However, it is a fact that they are independent of each other. This is evident, for example, in the equation (Ia) / (IIa) R 2 However, R in equation (Ib) / (IIb) 2 This means it is independent of R. 3 And this applies equally to all embodiments of the compounds according to the present invention. 2 and R 3 Furthermore, as a general rule, they are independent of each other.

[0032] Preferably, in the compounds of the present invention described as preferred above and / or below, 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.

[0033] R 2 and R 3 The aliphatic C1-C inside 12 The compounds according to the present invention, preferably those described above and / or below as preferred, are preferred, and the radicals independently include linear partial radicals, branched partial radicals, and / or cyclic partial radicals; preferably linear, branched, or cyclic.

[0034] R 2 and R 3 The aliphatic C1-C inside 12 The compounds according to the present invention, preferably those described above and / or below as preferred, are preferred, in which the radicals are independently saturated or unsaturated, preferably saturated.

[0035] R 2 and R 3 The aliphatic radicals inside are aliphatic C1-C 10 The compounds according to the present invention are preferably 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, and preferably those described as preferred above and / or below.

[0036] In some cases, R 2 and R 3 The aliphatic C1-C inside 12 Preferably, the compounds according to the present invention described above and / or below are preferred, wherein the radical independently represents one or more halogen substituents selected from the group consisting preferably of fluorine, chlorine, and bromine.

[0037] R 2 and R 3 Preferably, the compounds according to the present invention described above and / or below 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 12 carbon atoms, particularly preferably 6 to 10 carbon atoms, and most preferably 6 to 8 carbon atoms.

[0038] R 2 and R 3 Preferably, the compounds according to the present invention described above and / or below are preferred, wherein the aromatic radical therein independently represents one or more halogen substituents selected from the group consisting preferably of fluorine, chlorine, and bromine.

[0039] R 2 and R 3 Preferably, the compounds according to the present invention, as described above and / or below, are preferred, in which the halogen radical within is independently selected from the group consisting of fluorine, chlorine, and bromine.

[0040] R 2 and R 3 Preferably, the compounds according to the present invention, as described above and / or below, are preferred, wherein the ester radical, ketone radical, ether radical, and thioether radical contained therein independently contain 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 9 carbon atoms, even more preferably 1 to 7 carbon atoms, 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.

[0041] R 2 and R 3 A compound according to the present invention is preferred, preferably one described above and / or below, which independently contains 12 or fewer carbon atoms, preferably 10 carbon atoms, particularly preferably 6 carbon atoms, and very particularly 4 carbon atoms. This is, for example, R 3 While R has 10 or fewer carbon atoms, 2 This should be understood as meaning that it has six or fewer carbon atoms.

[0042] Listed radicals R 2 and R 3 This is particularly preferably already bonded by the selection of an appropriate starting compound.

[0043] Compounds according to the present invention, preferably those described above and / or below as preferred, are preferred, in which n and m are different or the same.

[0044] Substituent R 2 and R 3 The number and type of these elements, if selected, have a decisive effect on the solubility of the compounds according to the present invention in the rubber mixture and vehicle tires according to the present invention.

[0045] In formulas (Ia) and / or (IIa), m is zero, n is 1, and preferably R 3 aliphatic C1~C12 A radical compound according to the present invention is preferred. 3 The matters described above with respect to particularly preferred embodiments thereof are preferably applied mutatis mutandis. In many cases, such preferred compounds exhibit improved solubility in the rubber mixture according to the present invention and thus achieve the underlying objective particularly well. This, in particular, further reduces or completely prevents undesirable blooming.

[0046] Compounds according to the present invention are preferred in formula (Ib) and / or (IIb) in which m and n are zero. (For X) The cyclohexyl group already present in this compound similarly ensures improved solubility in the rubber mixture according to the present invention. In this case, R 3 Additional substituents in this form may preferably be omitted.

[0047] In relation to the present invention, a compound according to the present invention, wherein the compound has the structure of formula (IIa-I): [ka] (In the formula, - R 1 is aliphatic C3~C 12 A radical, preferably a C4-C8 alkyl group, - R 2 and R 3 They are either the same or different, and independently, Hydrogen, aliphatic C1-C 12 Radicals, aromatic radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals, preferably hydrogen and aliphatic C1-C 12 (Selected from a group consisting of radicals) Compounds having this feature are particularly preferred.

[0048] The matters described above (and also the following) relating to the compounds according to the present invention and their preferred embodiments also preferably apply mutatis mutandis to the preferred compounds of formula (IIa-I).

[0049] In the compound according to the present invention, radical R 1 teeth, - xi) Aromatic radicals, and - xii) Aliphatic C3~C 12 radical It is selected from the group consisting of the following.

[0050] In some cases, the aromatic radical in xi) is a substituent selected from the group consisting of alkyl radicals, halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals, and thioether radicals; particularly preferably, compounds according to the present invention, preferably those described above and / or below as preferred, are preferred, comprising alkyl radicals, 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. The substituents are preferably located at the meta or para position. The substituents are particularly preferably not at the ortho position. This is particularly advantageous for the lifespan of the aging stabilizer.

[0051] Preferably, the compounds according to the present invention described above and / or below are preferred, wherein 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.

[0052] Compounds according to the present invention described above and / or below as preferred, in which the aromatic radical in xi) is a phenyl radical (i.e., -C6H5), α-methylbenzyl (i.e., -CH2(CH3)-C6H5), and / or a benzyl radical (i.e., -CH2-C6H5), particularly preferably a phenyl radical.

[0053] xii) Aliphatic C3~C 12The radical comprises linear partial radicals, branched partial radicals, and / or cyclic partial radicals; preferably linear, branched, or cyclic, most preferably branched, and preferably the compounds according to the present invention as described above and / or below as preferred.

[0054] xii) Aliphatic C3~C 12 The compounds according to the present invention, preferably those described above and / or below as preferred, are preferred, in which the radical is saturated or unsaturated, preferably saturated.

[0055] 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, more preferably aliphatic C5-C7 radicals, and preferably those described as preferred above and / or below, are particularly preferred.

[0056] R 1 Preferably, the compounds according to the present invention, as described above and / or below, contain a tertiary carbon atom bonded to a nitrogen atom (N). The nitrogen atom (N) is preferably a secondary nitrogen atom.

[0057] 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.

[0058] R 1However, the compounds according to the present invention are particularly preferred, being branched or cyclic alkyl radicals that preferably contain 3 to 12 carbon atoms in each case, 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. In the case of cyclic alkyl groups, it is a fact that they preferably contain at least 5 carbon atoms, preferably at least 6 carbon atoms. This minimum number is preferably combined with the aforementioned upper limit regarding carbon atoms.

[0059] R 1 Compounds according to the present invention, preferably those described above and / or below as preferred, are highly preferred, and preferably contain 1,3-dimethylbutyl, phenyl, benzyl, or cyclohexyl, more preferably 1,3-dimethylbutyl. This provides particularly excellent protective effects in rubber mixtures, especially preferably for vehicle tires and rubber articles other than vehicle tires (preferably industrial rubber articles).

[0060] A compound according to the present invention, wherein the compound has the structure of formula (III): [ka] Compounds having this feature are very, particularly preferred.

[0061] The compound of formula (III) has sufficient 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 exhibits significantly 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 N-(1,3-dimethylbutylamino)-2-phenyl-1H-benzo[d]imidazole-6-amine.

[0062] Rubber mixtures containing the compound of formula (I): The present invention further relates to a rubber mixture comprising the compounds according to the present invention described above (preferably those described as preferred above and / or below), 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.

[0063] 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.

[0064] 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.

[0065] Particularly preferred are rubber mixtures according to the present invention, which preferably include one or more compounds according to the present invention as described above and / or below, selected from the group consisting of compounds of formula (I), (Ia), (Ib), (II), (IIa), (IIb), (IIa-I), and (III), particularly preferably including a compound of formula (IIa-I) and / or (III).

[0066] Preferably, the rubber mixture according to the present invention contains one or more compounds according to the present invention (preferably those described as preferred above), and is preferably one of the compounds described as preferred above and / or below, which is the only benzimidazole compound in the rubber mixture, and is particularly preferably a compound of formula (IIa-I) or (III), which is the only benzimidazole compound in the rubber mixture.

[0067] The rubber mixture according to the invention preferably contains the compound according to the invention in a total 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, very preferably 1 to 3 phr, preferably as described as preferred above and / or below.

[0068] As used in connection with this specification, the unit "phr" (parts per 100 parts by weight of rubber) is a unit of quantity for common mixing recipes in the rubber industry. The compounding quantity in parts by weight is based on 100 parts by weight of the total mass of all high molecular weight (M exceeding 20,000 g / mol) rubber. w ) rubber.

[0069] The rubber mixture according to the invention, preferably described as preferred above and / or below, preferably contains one or more diene rubbers. Diene rubbers are typically understood to mean rubbers formed by the polymerization or copolymerization of dienes and / or cycloalkenes, and thus having C=C double bonds either in the main chain or in side groups.

[0070] The diene rubber is selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), epoxidized polyisoprene (ENR), butadiene rubber (BR), butadiene-isoprene rubber, solution-polymerized styrene-butadiene rubber (SSBR), emulsion-polymerized styrene-butadiene rubber (ESBR), styrene-isoprene rubber, liquid rubber with a molecular weight M w 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, fluorine rubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-butadiene terpolymer, hydrogenated acrylonitrile-butadiene rubber, and hydrogenated styrene-butadiene rubber, preferably the rubber mixture according to the invention described as preferred above and / or below.

[0071] 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 / or from “non-Hevea” sources. Preferred non-Hevea sources are guayule shrubs and dandelions. Particularly preferred dandelions are TKS (Taraxacum Kok-saghyz; Russian dandelion).

[0072] The rubber mixture according to the present invention is particularly preferred, preferably one of the following, where 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).

[0073] The rubber mixture according to the present invention is most preferably one of the following, where 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).

[0074] 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.

[0075] 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 is preferably 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. Therefore, 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.

[0076] In some cases, the rubber mixture according to the present invention, preferably described as preferred above and / or below, is preferred, comprising one or more natural polyisoprenes (NR) and one or more synthetic polyisoprenes (IR). Therefore, a polyisoprene mixture is preferred.

[0077] In some cases, rubber mixtures according to the present invention, preferably those described above and / or below as preferred, are particularly preferred, comprising one or more natural polyisoprene (NR) in a total amount preferably 56 to 130 phr, particularly 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 in combination with 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.

[0078] In some cases, rubber mixtures according to the present invention, preferably as described above and / or below, are particularly preferred, containing one or more natural polyisoprene (NR) in a total amount significantly less than 100 phr. In these cases, the rubber mixture additionally contains one or more rubbers different from natural polyisoprene, preferably further diene rubbers, particularly preferably diene rubbers 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 containing one or more natural polyisoprene (NR) in a total amount of 5 to 55 phr, preferably 5 to 35 phr, more preferably 5 to 25 phr, and very 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.

[0079] In some cases, the rubber mixture according to the present invention, preferably as described above and / or below, is preferred, and preferably contains at least one type of butadiene rubber (BR, polybutadiene). 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.

[0080] In some cases, rubber mixtures according to the present invention, preferably as described above and / or below, are preferred, wherein the butadiene rubber is functionalized at the end groups 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.

[0081] A rubber mixture according to the present invention is preferred, preferably containing 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, as described above and / or below as preferred. This achieves particularly good tear and abrasion properties, as well as optimal braking characteristics, of the rubber mixture according to the present invention.

[0082] In some cases, rubber mixtures according to the present invention, preferably those described above and / or below as preferred, are preferred, comprising at least one styrene-butadiene rubber (styrene-butadiene copolymer). 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 connection with the present invention, the terms "styrene-butadiene rubber" and "styrene-butadiene copolymer" are used as synonyms. In some cases, rubber mixtures according to the present invention are preferred, wherein the styrene-butadiene rubber is functionalized at end groups and / or along the polymer chain by one or more functional groups. With respect to butadiene rubber, the matters described above apply mutatis mutandis to preferred functional groups.

[0083] Preferably, the rubber mixture according to the present invention contains 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, as described above and / or below. Particularly preferred is a rubber mixture according to the present invention that additionally contains one or more solution-polymerized styrene-butadiene rubbers (SSBR) 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 of the rubber mixture of the present invention. Particularly preferred is the use of solution-polymerized styrene-butadiene rubbers (SSBR) in combination with one or more additional rubbers. This typically achieves a balanced profile with improved properties.

[0084] 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.

[0085] Preferably, the rubber mixture according to the present invention, preferably as described above and / or below, contains an additional amount of one or more fillers, preferably 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.

[0086] 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.

[0087] 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 35-215 g / kg, particularly preferably 40-180 g / kg, and very preferably 45-140 g / kg, and / or a DBP value in accordance with ASTM D2414 in the range of 30-200 ml / 100g, preferably 70-170 ml / 100g, and particularly preferably 90-140 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.

[0088] In some cases, the rubber mixture according to the present invention is preferred, preferably having a total amount of carbon black in the rubber mixture 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 one or more silicon dioxide, particularly preferably silica.

[0089] In other cases, the rubber mixture according to the present invention, preferably as described above and / or below, is preferred, in which carbon black is present in the rubber mixture in a total amount in the range of 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 a sole filler or as a main filler (more than 50% by weight based on the total amount of filler, preferably in combination with a relatively small amount of silica).

[0090] Silicon dioxide is preferably amorphous silicon dioxide and / or calcined silicon dioxide. Particularly preferred amorphous silicon dioxide includes precipitated silica (also referred to as precipitated silicon dioxide).

[0091] 35 - 400 m 2 / g, preferably 50 - 350 m 2 / g, particularly preferably 85 - 320 m 2 / g, very preferably 120 - 235 m 2 / g of nitrogen surface area (BET surface area) (in accordance with DIN ISO 9277 and DIN 66132), and / or (preferably and) 30 - 400 m 2 / g, preferably 50 - 330 m 2 / g, particularly preferably 80 - 300 m 2 / g, very preferably 115 - 200 m 2 / g of CTAB surface area (in accordance with ASTM D3765) of amorphous silicon dioxide, preferably precipitated silica is particularly preferred. Such silicon dioxide brings particularly good physical properties of the vulcanized rubber in, for example, rubber mixtures for tire treads. The advantage in the processing of the mixture due to the shortening of the mixing time can also be brought about while maintaining the same product properties, resulting in improved productivity. Particularly preferred are Evonik's Ultrasil® VN3 (trade name) type silica, and highly dispersed silica (so-called HD silica). A preferred highly dispersed silica is Solvay's Zeosil® 1165MP.

[0092] In some cases, rubber mixtures according to the invention containing at least one silica, preferably in a total amount in the range of 30 - 500 phr, more preferably 50 - 400 phr, particularly preferably 80 - 300 phr, are preferred, preferably those described as preferred above and / or below. In these amounts, silica is present particularly 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).

[0093] In some cases, the rubber mixture according to the present invention, preferably described above and / or below as preferred, is preferred, which preferably contains at least one type of silica 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, the silica typically exists as a primary filler, preferably as an auxiliary filler in combination with carbon black.

[0094] A rubber mixture according to the present invention, preferably as described above and / or below, is particularly preferred, comprising at least one type of 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 7 to 40 phr.

[0095] Preferably, the rubber mixtures according to the present invention described as preferred above and / or below, preferably include additional fillers, i.e., fillers different from / not containing carbon black, silicon dioxide, and silica. These additional fillers preferably also include reinforcing fillers and / or non-reinforcing fillers.

[0096] 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.

[0097] 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.

[0098] In relation to the present invention, zinc oxide is not a filler for the purposes of the present invention.

[0099] Preferably, the rubber mixture according to the present invention, preferably as described above and / or below, contains one or more additional additives. Such additives are typically conventional additives, preferably added in typical amounts during at least one main mixing stage in the production of the rubber mixture.

[0100] One or more additional additives may preferably include the following: a) Anti-aging stabilizers different from the compounds of formula (I) according to the present invention and any other compounds according to the present invention that are 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 fatty acid esters and / or metal soaps, wherein the preferred metal soaps include 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.

[0101] In most cases, 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), and N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD) are essentially the same. A rubber mixture according to the present invention is particularly preferred if it is substantially free of, preferably free of, optionally free of, 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), more preferably substantially free of, preferably free of, optionally free of, paraphenylenediamine, preferably free of, optionally free of, dihydroquinoline, most preferably substantially free of, preferably free of, conventional aging stabilizers other than the compounds according to the present invention (i.e., conventional aging stabilizers known in the prior art), preferably free of, preferably free of, and preferably free of, the compounds according to the present invention described above and / or below as preferred. Therefore, a rubber mixture according to the present invention is particularly preferred to contain, preferably as the sole aging stabilizer, one or more compounds according to the present invention described above as preferred. In relation to the present invention, “substantially free” should be understood to mean a total amount in the range of a quantitative upper limit of 0.1 phr, preferably 0 phr to 0.1 phr, particularly preferably 0.0001 phr to 0.1 phr. An amount of zero (0), i.e. “free,” is particularly preferred. These very preferred low amounts, including zero (0) phr, make it possible to achieve equivalent protective effects with significantly reduced toxicity. The compounds according to the present invention replace the typically used paraphenylenediamines listed in the prior art. In some other cases, a rubber mixture according to the present invention is preferred in which an aging stabilizer different from the compounds according to the present invention (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.

[0102] 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, preferably described as preferred above and / or below, is preferred, comprising one or more dihydroquinolines, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), with or without the presence of paraphenylenediamine. The rubber mixture according to the present invention is preferably characterized by containing 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.

[0103] 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.

[0104] The silane coupling agent (see c) above) preferably includes any type known to those skilled in the art. Preferably, the rubber mixtures according to the present invention, as described above and / or below as preferred, preferably comprise one or more silane coupling agents. In some cases, the rubber mixtures according to the present invention preferably comprise a mixture of different silanes.

[0105] 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 mixing (in situ) or pretreatment (pre-modification).

[0106] 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.

[0107] 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®).

[0108] 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®.

[0109] Preferably, the rubber mixture according to the present invention, as described above and / or below, 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 more preferably 5 to 80 phr.

[0110] A rubber mixture according to the present invention, preferably as described above and / or below, is preferred, comprising one or more activators (see b above), preferably a zinc compound, 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.

[0111] The rubber mixture according to the present invention is preferably vulcanized or partially vulcanized, preferably vulcanized, and preferably as described above and / or below as preferred. This means that it is 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 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, it will be obvious to those skilled in the art that rubber mixtures are typically not in a vulcanized form until the final processing.

[0112] 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, preferably in combination with a vulcanization accelerator, wherein some of the vulcanization accelerator is preferably also a sulfur donor.

[0113] Preferably, the rubber mixtures according to the present invention, which contain sulfur and / or one or more sulfur donors, are those described above and / or below as 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.

[0114] 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.

[0115] 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).

[0116] A rubber mixture according to the present invention, preferably as described above and / or below, containing one or more vulcanization retarders, is preferred. The presence of vulcanization retarders contributes, for example, to a more balanced vulcanization process.

[0117] 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.

[0118] The rubber mixture according to the present invention is preferred for use in vulcanized products.

[0119] The rubber mixture according to the present invention is more preferable for use in vehicle tires, preferably in the outer or inner components of vehicle tires, and more preferably in the outer components.

[0120] Preferably, the rubber mixture according to the present invention, preferably as described above and / or below, comprises one or more strength members, preferably including fibers, fabrics and / or cords.

[0121] Vehicle tires containing the rubber mixture according to the present invention: The present invention further relates to a vehicle tire, preferably a pneumatic vehicle tire, comprising the rubber mixture described herein, preferably as described herein, in at least one component, preferably at least one outer component, wherein the outer component is preferably a tread, sidewall, and / or flange profile.

[0122] 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.

[0123] 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, in at least one component, a vulcanized rubber of at least one rubber mixture according to the present invention. It is known to those skilled in the art that most compounds in existence, such as rubber, exist in a chemically modified form, or may already be present after mixing, or only after vulcanization.

[0124] Preferably, the vehicle tires according to the present invention described as preferred above and / or below preferably include pneumatic vehicle tires and / or solid rubber tires.

[0125] Preferably, the vehicle tires according to the present invention described as preferred above and / or below are preferably selected from the group consisting of industrial and construction site vehicle tires, truck tires, passenger car tires and motorcycle tires.

[0126] Vehicle tires according to the present invention, preferably those described above and / or below as preferred, are particularly preferred, and which contain the rubber mixture according to the present invention as two, three, or more than three constituent components.

[0127] Use of the compound and rubber mixture according to the present invention: The present invention relates very generally to the use of compounds according to the present invention, preferably those described above as preferred, as aging stabilizers and / or (preferably and) antioxidants in rubber mixtures, preferably those described above as preferred, according to the present invention.

[0128] In addition, the present invention provides the compounds described above, preferably as preferred above and / or below, as aging stabilizers and / or antioxidants (preferably as aging stabilizers), preferably - Vehicle tires, especially 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 Regarding use in [location].

[0129] The foregoing provisions relating to the compounds (including preferred embodiments) and rubber mixtures (including preferred embodiments) according to the present invention also preferably apply mutatis mutandis to their use according to the present invention as aging stabilizers and / or antioxidants.

[0130] Preferred belts include conveyor belts.

[0131] 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 relation to use for engines.

[0132] The present invention also preferably comprises the rubber mixtures according to the present invention as described above and / or below. - Vehicle tires, preferably pneumatic vehicle tires, and / or - 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. This also relates to its use in the manufacture of [the product / service].

[0133] The foregoing provisions relating to the compounds (including preferred embodiments) and rubber mixtures (including preferred embodiments) according to the present invention preferably also apply mutatis mutandis to the use of the present invention for the above-mentioned manufacturing. The following provisions preferably also apply mutatis mutandis to vehicle tires according to the present invention.

[0134] Use for the manufacture of any tire components (including outer and / or inner components), preferably for the manufacture of outer components, particularly preferably for the manufacture of flange profiles, treads, and / or sidewalls. Use for the manufacture of caps for treads having a cap / base structure is particularly preferred. The type of component is preferably determined by different molding 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 and in an unvulcanized state are typically used for the manufacture of green tires. The green tires, which have not yet been vulcanized, are then preferably vulcanized.

[0135] 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.

[0136] Preferred belts include rubber belts and / or conveyor belts.

[0137] Method for producing the compound according to the present invention: The present invention further provides a method for producing a compound according to the present invention, preferably a compound of formula (I), i) Compounds of formula (B1): [ka] A process of generating or providing ii) The compound of formula (B1) - Hydrogen and ketones or aldehydes, preferably ketones, When reacted with, the compound of formula I) is formed: [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 an aromatic or aliphatic ring, - Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, aminos, and nitros, preferably aminos and nitros. process to obtain Regarding methods including

[0138] The foregoing relating to the compounds according to the present invention (preferably and especially as defined herein as preferred) also preferably applies mutatis mutandis to the manufacturing methods according to the present invention. This includes preferred embodiments and all the foregoing relating to the description of the compounds according to the present invention with respect to all levels of priority and possible combinations of these features, R 1 , R 2 , R 3 This means it applies to X, m, and n.

[0139] In Z, the halogen is chlorine, bromine, or iodine, and preferably chlorine. It is particularly preferable that fluorine is not present.

[0140] In Z, it is preferable that the sulfonate leaving group includes a triflate, nonaflate, mesylate, or tosylate.

[0141] Z is very preferably a nitro or amine. This means that a very preferred starting compound is the corresponding amino- or nitrobenzimidazole, and X is particularly preferably a phenyl ring or a cyclohexyl ring. Thus, the foregoing provisions relating to the compounds of formulas (Ia), (Ib), (IIa) and (IIb) according to the present invention are particularly preferred to apply.

[0142] The method according to the present invention, preferably described above and / or below as preferred, is preferred, wherein the reaction with hydrogen in step ii) is carried out using a catalyst, preferably using a hydrogenation catalyst. This means that step ii) preferably uses or employs such a catalyst. In some cases, “hydrogenation catalyst” is also called “hydrogenation catalyst,” and in relation to the present invention, both terms have the same scope of definition.

[0143] In step ii), the method according to the present invention, preferably as described above and / or below, is preferred, wherein the catalyst, preferably a hydrogenation catalyst, comprises 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.

[0144] Metals, preferably noble metals, are used, preferably on carbon (C). Particularly preferred catalysts include palladium-carbon (Pd / C), platinum-carbon (Pt / C), Raney nickel, and / or copper chromate, with palladium-carbon (Pd / C) and / or platinum-carbon (Pt / C) being particularly preferred. Pt / C catalysts have been found to have the advantage of being able to similarly convert mixtures of amino- and nitrobenzimidazoles, and thus achieving a more complete conversion. In contrast, Pd / C catalysts are particularly preferred for reacting aminobenzimidazoles, but less preferred for the corresponding nitrobenzimidazoles.

[0145] The method according to the present invention, preferably as described above and / or below, is preferred, wherein the reaction with hydrogen in step ii) takes place over a period of 1 to 30 hours, preferably 3 to 22 hours, particularly preferably 5 to 16 hours, and most preferably 8 to 13 hours.

[0146] The method according to the present invention, preferably as described above and / or below, is preferred, wherein the reaction with hydrogen in step ii) is carried out in a pressure reactor, preferably in an autoclave.

[0147] A method according to the present invention, wherein the reaction in step ii) - This is done using a catalyst; and / or (preferably and) - The process is carried out at a temperature of 40°C to 190°C, preferably 55°C to 170°C, particularly preferably 70°C to 150°C, particularly preferably 85°C to 130°C; and / or (preferably and) - The method according to the present invention is particularly preferred if it is carried out at a pressure of 20 to 70 bar, preferably 28 to 57 bar, and especially preferably 35 to 45 bar.

[0148] In the method according to the present invention, the ketone in step ii) subsequently becomes the radical R 1It 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 solvent used in step ii) is preferably the same as the ketone / aldehyde, or different from (preferably the same as) the ketone / aldehyde, preferably the method according to the present invention as described above and / or below as preferred.

[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 not in liquid form under the reaction conditions, 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 preferably used as a reactant only in the amount stoichiometrically required (in some cases, preferably in a slight excess).

[0151] The method according to the present invention, preferably as described above and / or below, is particularly preferred, wherein the ketone / aldehyde, particularly preferably the ketone, is in liquid form in step ii) and particularly preferably present as the 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, preferably as described above and / or below, is preferred, which involves one or more purification steps, preferably filtration, chromatography, recrystallization, and / or washing with a solvent, following step ii). 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] The present invention will now be described more specifically using 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: First step (synthesis of 2-phenyl-1H-benzo[d]imidazole-6-amine): 2-phenyl-1H-benzo[d]imidazole-6-amine was prepared according to C. Diaz, J. Comput. Aided Mol Des., 2015, 29, 143-154. This yielded a mixture containing the amine (80%) and the corresponding nitro compound (20%).

[0155] Second stage (N-(1,3-dimethylbutylamino)-2-phenyl-1H-benzo[d]imidazole-6-amine): The mixture obtained in step 1 was converted in step 2 using a platinum-carbon (Pt / C) catalyst according to the following scheme. [ka] 0.80 g (3.82 mmol, 0.8 equivalents) of 2-phenyl-1H-benzo[d]imidazole-6-amine, 0.20 g (0.84 mmol, 0.2 equivalents) of 6-nitro-2-phenyl-1H-benzo[d]imidazole, 0.40 g of platinum-carbon (5%; 0.4 g supported on a 4.67 mmol substrate), and 20.0 ml of methyl isobutyl ketone (MIBK) were weighed into a stainless steel autoclave equipped with a teflon in-liner. The reaction mixture was then subjected to hydrogen at a pressure of 40 bar and stirred at 120°C for 10 hours. After the reaction was complete, excess hydrogen was released. The resulting reaction product was a suspension, which was filtered through Celite and subsequently washed with ethanol. The resulting filtrate was concentrated until dry and then further dried under reduced pressure. The resulting dried product was purified by column chromatography (dichloromethane / methanol; 100:0 → 95:5). The purified product was a reddish-brown solid; yield 0.31 mg (23% of the theoretical value). 1 H-NMR(500MHz,DMSO-d6)δ=12.28(s,1H),8.06(d,J=7.8Hz,2H),7.49(t,J=7.6Hz,2H), 7.40(t,J=7.5Hz,1H),7.35-7.30(m,1H),6.56(d,J=10.4Hz,2H),4.36(t,1H),3.45(tt, J=6.8,4.1Hz,1H),1.78(dh,J=13.5,6.8Hz,1H),1.50(dt,J=13.8,7.0Hz,1H),1.23(dt, J=13.7,6.9Hz,1H),1.13(d,J=6.2Hz,3H),0.95(d,J=6.6Hz,3H),0.89(d,J=6.6Hz,3H). 13 C-NMR(126MHz,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. Mass spectrometry results: ESI-MS[M+H] + =294.

[0156] Measurement of 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.

[0157] 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 = 54,000 g / mol, glass transition temperature T g The mixture was heated to 180°C (at -63°C) until oxidation began. The time required for this is the "oxidation induction time" mentioned above in this invention.

[0158] 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).

[0159] 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).

[0160] 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.

[0161] [Table 1]

[0162] Table 1 shows that the compound of formula (III) achieves a significantly improved protective effect compared to 6PPD, particularly at a temperature of 180°C, which is considered harsh due to the unexpectedly long time required for oxidation to become detectable. The experimentally observed improvement here is approximately 100%.

[0163] Generally, compounds of formula (I) and especially those of formula (III) are based on the benzimidazole basic structure, particularly the 2-phenylbenzimidazole basic structure. In comparison, 6PPD is based on the diphenylamine basic structure. Benzimidazole or phenyl-benzimidazole has significantly lower environmental and health hazards.

[0164] 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 compounds, but also poses less harm to health. Furthermore, the compound / classification of compounds according to the present invention also achieves superior protective effects.

[0165] As a representative example of the compound according to the present invention represented by formula (I), the compound according to the present invention represented by formula (III) also exhibits sufficient solubility in rubber mixtures.

[0166] In supplementary tests, solubility was further improved when the phenyl ring had an alkyl substituent or when the phenyl ring was completely hydrated (data not shown).

[0167] 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).

[0168] 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.

[0169] 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. References (ref.) are for no anti-aging stabilizer.

[0170] In all mixtures, the total amount of aging stabilizer (6PPD or compound of formula (III)) and plasticizer oil MES is 10 phr.

[0171] [Table 2]

[0172] 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). In contrast, the reference material shows completely 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 an aromatic or aliphatic ring.)

2. The compound according to claim 1, wherein X comprises six carbon atoms, preferably a phenyl radical or a cyclohexyl radical.

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

4. The compound has the structure of formula (IIa) or (IIb). 【Transformation 3】 It has, in the formula, R １ , R ２ , R ３ The compound according to any one of claims 1 to 3, wherein 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 are the same or different.

6. In formulas (Ia) and / or (IIa), m is 0, n is 1, and preferably R ３ is aliphatic C １ ~C １２ The compound according to claim 4 or 5, which is a radical.

7. The compound according to claim 4 or 5, wherein m and n are 0 in formula (Ib) and / or (IIb).

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

9. The structure of equation (III) is 【Chemistry 4】 A compound according to any one of claims 1 to 8, comprising:

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

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

12. A compound according to any one of claims 1 to 9, preferably as an anti-aging stabilizer and / or antioxidant. - Vehicle tires, especially 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].

13. - Vehicle tires, preferably pneumatic vehicle tires, and / or - 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. Use of the rubber mixture according to claim 10 for manufacturing the product.

14. A method for producing the compound of formula (I), i) Compound of formula (B1): 【Transformation 5】 A process of generating or providing ii) The compound of formula (B1) above, - Hydrogen and ketones or aldehydes, preferably ketones, When reacted with, the compound of formula I) is obtained: 【Transformation 6】 (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 an aromatic or aliphatic ring, - Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, aminos, and nitros, preferably aminos and nitros. process to obtain A method that includes this.

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

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