Compounds for use as antioxidants in rubber mixtures and vehicle tires

Abstract

The present invention is defined in more detail in the text, as formula (I) The present invention relates to the compound of TIFF2026520410000018.tif17170, a rubber mixture containing the compound, a vehicle tire comprising the rubber mixture as at least one component, a process for preparing the compound, and the use of the compound as an anti-aging agent and / or antioxidant.

Description

[Technical Field]

[0001] The present invention is further defined in the text as formula (I) [ka] The present invention relates to a compound, a rubber mixture containing this compound, a vehicle tire comprising the rubber mixture as at least one component, a process for producing this 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 articles other than vehicle tires (preferably industrial 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 generally in many cases at high temperatures during their intended use. Depending on the type of polymer / long-chain compound, they may undergo chain shortening (until the article liquefies) or the material / article may undergo subsequent undesirable hardening.

[0003] Therefore, aging stabilizers make a decisive contribution 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, a drawback of the aforementioned compounds is 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 the anti-aging stabilizer have relatively low solubility in the polymer matrix surrounding the tire / rubber article, they diffuse onto its surface, often forming a film there that has a color usually distinguishable from the rest of the article. In the case of vehicle tires, this typically manifests as a brown discoloration on the normally black sidewall. In addition to the aesthetic drawback, this is also related to the 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 also causes further molecules of the anti-aging stabilizer to diffuse toward the surface, resulting in a continuous decrease in the level of protection.

[0007] Anti-aging stabilizers in rubber compositions are, of course, well-known. For example, Japanese Patent Publication No. 6049236B2 discloses a phosphorus-containing anti-aging stabilizer. [Overview of the project] [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, specifically novel compounds that have sufficient solubility in their respective matrices, such as polymers, and have lower potential hazards. This is intended to minimize or further prevent the tendency to bloom while ensuring continuous and optimal protection from oxygen, free radicals and / or (preferably and) ozone, and reducing health hazards.

[0009] The compound is also intended to ensure at least sufficiently comparable aging stability to known aromatic amines such as 6PPD. [Means for solving the problem]

[0010] This problem is related to formula (I) according to the present invention: [ka] (In the formula, - R 1 teeth, - xi) Aromatic group, and - xii) Aliphatic C3~C 12 base Selected from the group consisting of, - R 2 and R 3 They are either the same or different, and aliphatic C1-C 12 A group independently selected from the group consisting of a group, aromatic group, halogen group, cyano group, ester group, ketone group, ether group and thioether group, - R 4 is aliphatic C1-C 20 Groups and aromatic C5~C 20 Selected from a group consisting of elements, - X represents oxygen or sulfur, preferably oxygen. - m is 0, or 1, or 2, or 3, and (n is 0, 1, 2, 3, or 4) is solved by the compound of

[0011] The compound of formula (I) according to the present invention is a phenophosphazinine derivative and has potentially lower risk compared to known anti-aging stabilizers based on aniline and its decomposition products as suggested by the initial studies on related compounds (Yin Zhi Gang et al. Dyes and Pigments, 2009, 81(2), 137 - 143). In vehicle tires and rubber articles different from vehicle tires (preferably industrial rubber articles), this is an obvious advantage because the rubber components are often released by wear / other decomposition processes.

[0012] The compound of formula (I) according to the present invention shows at least equivalent / sufficiently similar anti-aging stability, especially in rubber mixtures / vehicle tires, compared to the known commonly used anti-aging stabilizer 6PPD (see the following examples).

[0013] The compound of formula (I) according to the present invention is preferably an anti-ozone agent, and more preferably is also an anti-ozone agent in addition to being capable of reacting with oxygen and / or free radicals (preferably as described above).

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

[0015] The subscripts m and n represent the number of the corresponding groups R 2 and R 3 When m or n is 0 (zero), the group 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 present invention.

[0016] Similarly, (R 2 ) m and NHR 1 Bonding to the four possible carbon atoms in the corresponding 6-membered ring, as well as (R 3 ) n It will 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 the adjacent ring. These groups are located at any position in the respective ring to which they are assigned, except that in each case they are at any position in which two or more identical positions are simultaneously located. In connection with the present invention, the group 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 "group" should be understood as referring to a group 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 any particular description.

[0019] The compound of formula (I) according to the present invention has sufficient to 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 presence of group R 2 , R 3 and / or R 4 Further optimization is achieved through the selection of suitable components. This minimizes or virtually prevents undesirable blooming of the compound, which is therefore advantageous for its aging stabilization effect. Less blooming of the aging stabilizer means less of the aging stabilizer is lost from the surface, intentionally or unintentionally, and therefore less subsequent diffusion of the aging stabilizer. This also brings significant benefits to the environment. [Modes for carrying out the invention]

[0020] The present invention encompasses all preferred embodiments, particularly those reflected in the claims. The present invention 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] In addition, all information relating to the characteristics of the compounds according to the present invention also applies to the processes according to the present invention for producing the compounds, the rubber mixtures according to the present invention containing the compounds, and the uses according to the present invention.

[0022] Compound according to the present invention: Formula (II): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 (where X, m, and n are defined as claimed in claim 1, and preferably as preferred in the text.) Compounds according to the present invention having the structure are preferred.

[0023] In relation to the present invention, X represents oxygen (i.e., O) or sulfur (i.e., S). Compounds according to this specification, preferably those described as preferred above and / or below, in which X is oxygen, are particularly preferred.

[0024] The descriptions made in this text relating to the compound of formula (I) are, in particular, also applicable mutatis mutandis 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 to excellent solubility, especially in rubber mixtures for vehicle tires.

[0025] Compounds according to the present invention described above and / or below are particularly preferred, preferably where n and m are the same or different, preferably the same.

[0026] The compounds according to the present invention, preferably those described as preferred above and / or below, are preferred, in which n and m are zero.

[0027] In relation to the present invention, R 2 and R 3 These are, in principle, independent of each other. In the compounds according to the present invention, preferably, as described above and / or below, the group R 2 and R 3 They are either the same or different, and aliphatic C1-C 12 A group is independently selected from the group consisting of a group, an aromatic group, a halogen group, a cyano group, an ester group, a ketone group, an ether group, and a thioether group.

[0028] R 2 and R 3 The aliphatic C1-C inside 12 Compounds according to this specification are preferred, wherein the groups independently comprise linear subgroups, branched subgroups and / or cyclic subgroups, and are preferably linear, branched, or cyclic, as described above and / or below.

[0029] R 2 and R 3 The aliphatic C1-C inside 12 Compounds according to this specification are preferred in which the groups are independently saturated or unsaturated, preferably saturated, and preferably as described above and / or below.

[0030] R 2 and R 3 The aliphatic group inside is aliphatic C1-C 10 Compounds according to this specification are preferred, preferably having a group, preferably an aliphatic C1-C8 group, more preferably an aliphatic C1-C6 group, particularly preferably an aliphatic C1-C4 group, most particularly preferably an aliphatic C1-C2 group, preferably methyl and / or ethyl.

[0031] In some cases, R 2 and R 3 The aliphatic C1-C inside12 Compounds according to this specification are preferred, preferably those described above and / or below, in which the group independently comprises one or more halogen substituents selected from the group consisting of fluorine, chlorine, and bromine.

[0032] R 2 and R 3 The compounds according to this specification are preferred, preferably those described as preferred above and / or below, in which the aromatic group contains independently 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.

[0033] R 2 and R 3 The compounds according to this specification are preferred, preferably those described above and / or below, in which the aromatic group therein independently contains one or more halogen substituents selected from the group consisting of fluorine, chlorine, and bromine.

[0034] R 2 and R 3 The compounds according to this specification are preferred, in which the halogen group therein is independently selected from the group consisting of fluorine, chlorine, and bromine, preferably as described above and / or below.

[0035] R 2 and R 3 Compounds according to this specification are preferred, preferably those described as preferred above and / or below, in which the ester group, ketone group, ether group, and thioether group in the compound 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.

[0036] R 2 and R 3However, compounds according to this specification that independently contain a maximum of 12 carbon atoms, preferably 10 carbon atoms, particularly preferably 6 carbon atoms, and most particularly preferably 4 carbon atoms, are preferred, as described above and / or below. For example, R 3 While R has a maximum of 10 carbon atoms, 2 This should be understood as meaning that it has a maximum of 6 carbon atoms.

[0037] Enumerated bases R 2 and R 3 This is, in particular, already bonded by the selection of a suitable starting compound.

[0038] Substituent R 2 and R 3 The number and type of, 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. Preferably, instead of or in addition to, R 4 This also applies to...

[0039] base R 4 is aliphatic C1-C 20 Groups and aromatic C5~C 20 Selected from a group consisting of elements.

[0040] R 4 is aromatic C5~C 18 Group, preferably aromatic C5-C 16 C5-C, more preferably aromatic 14 Base, particularly preferably aromatic C6-C 12 The base, and especially preferably aromatic C6-C 10 The compounds according to this specification, which are preferably the group described above and / or below as preferred, are preferred.

[0041] Aromatic C5~C 20 It is especially preferred when the group is phenyl or benzyl.

[0042] R 4 However, aliphatic C1~C 18A group, preferably an aliphatic C2-C 16 group, more preferably an aliphatic C3-C 14 group, particularly preferably an aliphatic C4-C 12 group, very particularly preferably an aliphatic C5-C 10 group. The compounds according to the invention are preferred. This is preferably applied instead of or in combination with the aromatic C5-C 4 group in R 20 and its preferred embodiments.

[0043] R 4 is a C1-C 20 alkyl group, preferably a C1-C 18 alkyl group, more preferably a C2-C 16 alkyl group, particularly preferably a C3-C 14 alkyl group, very particularly preferably a C4-C 12 alkyl group, most preferably a C5-C 10 alkyl group. The compounds according to the present specification, which are preferably described as preferred above and / or below, are particularly preferred. This is preferably also applied instead of or in combination with the aromatic C5-C 4 group in R 20 and its preferred embodiments.

[0044] R 4 is heptyl, octyl, nonyl, benzyl or phenyl. The compounds according to the invention are very particularly preferred.

[0045] In the compounds according to the invention, the group R 1 is - xi) an aromatic group, and - xii) an aliphatic C3-C 12 group selected from the group consisting of.

[0046] In some cases, the compounds according to the present invention are preferred, wherein the aromatic group in xi) comprises substituents selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups, particularly preferably ester groups, ketone groups, ether groups, and thioether groups, preferably as described above and / or below. In other cases, particularly preferably, the aromatic group 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.

[0047] The compounds according to the present invention are preferred, wherein the aromatic group 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, as described above and / or below.

[0048] The compounds according to the present invention are preferred in which the aromatic group in xi) contains a phenyl group (i.e., -C6H5), alpha-methylbenzyl (i.e., -CH2(CH3)-C6H5) and / or a benzyl group (i.e., -CH2-C6H5), particularly preferably a phenyl group, and are preferably as described above and / or below.

[0049] xii) Aliphatic C3~C 12 The compounds according to the present invention are preferred, wherein the group comprises a linear subgroup, a branched subgroup and / or a cyclic subgroup, preferably linear, branched or cyclic, most preferably branched, and preferably as described above and / or below.

[0050] xii) Aliphatic C3~C 12 Compounds according to the present invention are preferred in which the group is saturated or unsaturated, preferably saturated, and preferably as described above and / or below.

[0051] In xii), the aliphatic group is aliphatic C3-C 10The radical is preferably an aliphatic C4 - C8 radical, more preferably an aliphatic C5 - C7 radical, and the compounds according to the invention, which are preferably described as preferred above and / or below, are preferred.

[0052] R 1 contains a tertiary carbon atom bonded to a nitrogen atom (N), and the compounds according to the invention, which are preferably described as preferred above and / or below, are preferred. The nitrogen atom (N) is preferably a secondary nitrogen atom.

[0053] In connection with the present invention, the term "tertiary carbon atom" is to be understood as meaning a carbon atom having only one hydrogen atom bonded to it. Compared with secondary and quaternary carbon atoms, this preferably brings about a particularly excellent protective effect in rubber mixtures (particularly preferably in vehicle tires and / or other rubber articles different from vehicle tires (particularly industrial rubber articles)). A reactivity optimized with respect to the mechanism related to stabilization against aging is particularly realized, whereby unwanted side reactions are avoided.

[0054] R 1 is a branched or cyclic alkyl radical containing 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. The compounds according to the invention are particularly preferred. These are particularly preferably saturated. For cyclic alkyl radicals, they are preferred when they contain at least 5 carbon atoms, preferably at least 6 carbon atoms. This minimum number is preferably combined with the aforementioned upper limit for carbon atoms.

[0055] R 1 is 1,3 - dimethylbutyl, phenyl, benzyl or cyclohexyl, preferably 1,3 - dimethylbutyl, and the compounds according to the invention, which are preferably described as preferred above and / or below, are extremely particularly preferred. Thereby, a particularly excellent protective effect in rubber mixtures for rubber mixtures, particularly preferably in vehicle tires and rubber articles different from vehicle tires (preferably industrial rubber articles), is obtained.

[0056] Formula (III): [ka] Compounds according to the present invention having the above characteristics are extremely preferred.

[0057] The compound according to formula (III) has sufficient solubility in polymers, preferably rubber mixtures, and particularly preferably rubber mixtures of vehicle tires and rubber articles other than vehicle tires (preferably industrial rubber articles). Furthermore, the compound according to formula (III) can be produced by a relatively simple, energy-efficient, and low-cost method, and exhibits a sufficiently superior protective effect compared to 6PPD (see the examples below). According to IUPAC nomenclature, the compound according to the present invention of formula (III) is also referred to as follows. 2-(1,3-dimethylbutylamino)-10-octyl-5H-phenophosphadinine-10-oxide.

[0058] Rubber mixtures containing compounds according to formula (I): The present invention further relates to a rubber mixture containing the compounds according to the present invention described above (preferably those described as preferred above and / or below, particularly preferably compounds according to formula (III)), and preferably one or more diene rubbers. The rubber mixture preferably contains one or more compounds according to the present invention, and at least one of the rubbers is a diene rubber.

[0059] The aforementioned matters relating to the compounds of the present invention described above as particularly preferred are preferably also applicable mutatis mutandis to the rubber mixtures of the present invention.

[0060] 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.

[0061] A rubber mixture according to the present invention is preferred, which contains one or more compounds according to the present invention (preferably those described as preferred above), and which preferably consists of the sole phenophosphadinine oxide in the rubber mixture, preferably as described above and / or below.

[0062] A rubber mixture according to the present invention is preferred, preferably containing the compound of the present 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, and most particularly preferably 1 to 3 phr, as described above and / or below.

[0063] The unit "phr" (parts per 100 parts by weight of rubber) as used herein is a unit of quantity for common mixing recipes in the rubber industry. The amount of parts by weight is the total amount of all high molecular weight (M20,000 g / mol or more) present in the mixture. w The total mass of rubber is based on 100 parts by weight.

[0064] Preferably, the rubber mixtures according to the present invention, as described above and / or below, preferably comprise 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 a side group.

[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. wPreferably, the rubber mixture according to the present invention is selected from the group consisting of liquid rubber with a content 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, preferably as described above and / or below.

[0066] In relation to the present invention, the term “natural rubber” should be understood to mean natural rubber obtained from the Hevea rubber tree and / or “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, wherein the diene rubber is selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR), emulsion-polymerized styrene-butadiene rubber (ESBR), butyl rubber (IIR), and halobutyl rubber (XIIR), preferably as described above and / or below.

[0068] The rubber mixture according to the present invention is particularly preferred, wherein the diene rubber is selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR), and emulsion-polymerized styrene-butadiene rubber (ESBR), preferably as described above and / or below.

[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 rubber articles for straps, drive belts, hoses, belts, and / or 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] Preferably, polyisoprene includes cis-1,4-polyisoprene and / or 3,4-polyisoprene. This applies whether the polyisoprene is natural or synthetic. 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.

[0071] 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.

[0072] In some cases, rubber mixtures according to the present invention 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 particularly preferably 90 to 110 phr, and more preferably 95 to 100 phr, as described above and / or below. 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, the rubber mixture according to the present invention is preferred, which contains one or more natural polyisoprene (NR) in a total amount significantly less than 100 phr, preferably as described above and / or below. 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, the rubber mixture according to the present invention is particularly preferred, 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 most particularly preferably 5 to 20 phr. 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 is preferred, preferably comprising at least one butadiene rubber (BR, polybutadiene) as described above and / or below. Butadiene rubbers comprising high-cis and / or low-cis types are 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. 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 yield particularly excellent properties of the rubber mixture, especially low hysteresis.

[0075] In some cases, the rubber mixtures according to the present invention are preferred, in which butadiene rubber is functionalized end-group and / or along the polymer chain using one or more functional groups, preferably as described above and / or below. It is preferred that 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 aforementioned groups. In some cases, the functional groups preferably include one or more metals.

[0076] The 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. This achieves particularly good tear and abrasion properties and optimal braking characteristics of the rubber mixture according to the present invention.

[0077] In some cases, rubber mixtures according to the present invention, preferably as described above and / or below, 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 above-mentioned matters apply mutatis mutandis to preferred functional groups.

[0078] A rubber mixture according to the present invention is preferred, preferably comprising 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. A rubber mixture according to the present invention is particularly preferred, wherein one or more solution-polymerized styrene-butadiene rubbers (SSBRs) are additionally present in a total amount of 10 to 80 phr, preferably 30 to 75 phr, and particularly preferably 50 to 70 phr. This achieves particularly good rolling resistance characteristics 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 preferably preferably described as preferred above and / or below, and further preferably containing one or more fillers 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 blacks include, in principle, any type 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] Carbon black is preferred when it 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 particularly 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 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 most particularly preferably 5 to 15 phr, preferably as described above and / or below. At these amounts, the carbon black typically exists as an auxiliary filler in combination with a main filler, which is preferably one or more silicon dioxide, particularly preferably silica.

[0084] In other cases, the rubber mixture according to the present invention is preferred, preferably having carbon black 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, as described above and / or below. In these amounts, the carbon black is present particularly as the sole filler or 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 is precipitated silica (also called precipitated silicon dioxide).

[0086] 35-400m 2 / g, preferably 50-350mg 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, most preferably 115-200m 2Amorphous silicon dioxide having a CTAB surface area of ​​1 / g (according to ASTM D3765), preferably precipitated silica, is particularly preferred. Such silicon dioxide yields particularly good physical properties of vulcanized rubber in rubber mixtures for tire treads, for example. Advantages in processing the mixture due to reduced 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, preferably containing at least one type of silica in a total amount in the range of preferably 30 to 500 phr, preferably 50 to 400 phr, and particularly preferably 80 to 300 phr. In these amounts, the silica is present, in particular, as the sole filler or 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, preferably containing at least one type of silica in a total amount in the range of preferably 5 to 100 phr, particularly 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, preferably carbon black.

[0089] A rubber mixture according to the present invention 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, preferably as described above and / or below.

[0090] The rubber mixture according to the present invention preferably comprises additional fillers, namely carbon black, silicon dioxide, and silica, and fillers that are different from or do not contain them, as described above and / or below as preferred. These additional fillers preferably 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." Preferred carbon nanotubes 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 this specification, zinc oxide is not one of the fillers within the scope of the present invention.

[0094] A rubber mixture according to the present invention is preferred, preferably containing one or more further additives, as described above and / or below. Such additives are typically conventional additives that are preferably added in typical amounts during at least one main mixing stage in the production of the rubber mixture.

[0095] Preferably, one or more additional additives include the following: a) A aging stabilizer that is known in the prior art and is different from the compound of formula (I) according to the present invention and any other compound according to the present invention, preferably comprising paraphenylenediamine and / or dihydroquinoline, and particularly preferably selected from the group consisting of N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine (SPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), and 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 one 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 (mild extraction 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 20000 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 (mild extraction solvate), and naphthenic oils.

[0096] In most cases, these are 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). A rubber mixture according to the present invention is particularly preferred, substantially free, preferably free, optionally free of 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), more preferably substantially free of paraphenylenediamine, preferably free, optionally free of dihydroquinoline, most preferably substantially free of aging stabilizers different from the compounds according to the present invention (i.e., conventional aging stabilizers known in the prior art), preferably free, preferably as described above and / or below. 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 as described above. 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 para-phenylenediamines listed in the prior art. In some other cases, a rubber mixture according to the present invention is preferred in which a different aging stabilizer than the compounds according to the present invention (particularly para-phenylenediamine) 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, i.e., desirable in some cases and undesirable in others. In some cases, the rubber mixture according to the present invention is preferred, preferably containing one or more dihydroquinolines, preferably 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), (whether or not paraphenylenediamine is present), as described above and / or below. The rubber mixture according to the present invention is preferred if it contains 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 the aging stabilizer in a) is present or not.

[0099] The silane coupling agent (see c above) is preferably any type known to those skilled in the art. Preferably, the rubber mixture according to the present invention, as described above and / or below as preferred, 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 surface silanol groups or other polar groups of silicon dioxide (especially silica) before being added to the rubber during the mixing of rubber / rubber mixtures or during pretreatment (pre-modification).

[0101] Preferred silane coupling agents include bifunctional organosilanes having at least one alkoxy group, cycloalkoxy group, or phenoxy group as a leaving group on the silicon atom, and further including a functional group that can chemically react with the polymer's double bond (optionally after dissociation). Preferred groups include -SCN, -SH, -NH2 and / or -S x-(x=2~8) are examples. 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 (trade name X50S®, manufactured by Evonik).

[0103] Alternatively or in addition, 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, 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] A rubber mixture according to the present invention is preferred, preferably one or more further additives present in a total amount ranging from 3 to 150 phr, preferably 4 to 100 phr, and particularly preferably 5 to 80 phr, as described above and / or below.

[0105] A rubber mixture according to the present invention is preferred, preferably comprising one or more activators (see b above), preferably a zinc compound, particularly preferably zinc oxide, and preferably as described above and / or below. Preferably, there are no restrictions on the type of zinc oxide. Granules and / or powder are preferred. The zinc oxide is preferably up to 100 ml 2 / 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] A rubber mixture according to the present invention is preferred if it is vulcanized or partially vulcanized, preferably vulcanized, preferably as described above and / or below. 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 connection with the present invention, the terms “vulcanized” and “crosslinked” are used as synonyms. Therefore, a 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 state 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, preferably 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, preferably as described above and / or below, comprising sulfur and / or one or more sulfur donors, is preferred. Since there are no specific restrictions on the sulfur donor, all sulfur donors known to those skilled in the art are intended in principle, provided that they supply sulfur in an appropriate 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, preferably containing one or more vulcanization retarders, is preferred, as described above and / or below. 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 provided, 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, i.e., preferably the total amounts of sulfur, sulfur donor, vulcanization accelerator and vulcanization retarder. The vulcanizing system is added in the final mixing step to obtain the finished mixture, which is preferably subjected to further processing by extrusion and / or calendering to obtain the desired shape. The shape thus obtained preferably determines the subsequent application, such as use in vehicle tires.

[0113] The rubber mixture according to the present invention is preferred for use in vulcanized rubber.

[0114] The rubber mixture according to the present invention is very preferable for use in vehicle tires, preferably in the outer or inner components of vehicle tires, preferably in the outer components.

[0115] Preferably, the rubber mixture according to the present invention is preferably described as preferred above and / or below, and preferably includes one or more strength members including fibers, cloth and / or cords.

[0116] 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 as preferably described herein as preferred in at least one component, preferably at least one outer component, wherein the outer component is preferably a tread, sidewall and / or flange profile.

[0117] 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.

[0118] The vehicle tire according to the present invention is preferably vulcanized, i.e., 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 present, such as rubber, are or may be present in a chemically modified form already after mixing or only after vulcanization.

[0119] Preferably, the vehicle tires according to the present invention, as described above and / or below as preferred, preferably include pneumatic vehicle tires and / or solid rubber tires.

[0120] Preferably, the vehicle tires according to the present invention, as described 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.

[0121] A vehicle tire according to the present invention, preferably as described above and / or below, is particularly preferred, comprising two, three, or four or more components of the rubber mixture according to the present invention.

[0122] Use of the compound and rubber mixture according to the present invention: The present invention relates very generally to the use of the compounds according to the present invention, preferably as described above as preferred, in rubber mixtures, preferably as aging stabilizers and / or (preferably and) as antioxidants in rubber mixtures according to the present invention (preferably as described above as preferred).

[0123] In addition, the present invention preferably, - Vehicle tires, especially preferably pneumatic vehicle tires, - Particularly preferred are 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 robotics applications, soles and parts of soles, vehicle tires and different rubber articles. - Oil and / or grease, and / or - Fuel and / or lubricant This relates to the use of the compounds according to the present invention, preferably those described above as preferred, as aging stabilizers and / or antioxidants (preferably aging stabilizers) in the context of [unclear text].

[0124] The foregoing statements relating to the compounds according to the present invention (including preferred embodiments) and the foregoing statements relating to the rubber mixtures 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.

[0125] A preferred type of belt is a conveyor belt.

[0126] 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 preferably used in connection with engines.

[0127] The present invention - Vehicle tires, preferably pneumatic vehicle tires, and / or - Particularly preferred are 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 robotics applications, soles and parts of soles, vehicle tires and different rubber articles. The present invention also relates to the use of rubber mixtures, preferably as described above and / or below, for the manufacture of the present invention.

[0128] The foregoing statements relating to the compounds according to the present invention (including preferred embodiments) and the foregoing statements relating to the rubber mixtures according to the present invention (including preferred embodiments) preferably also apply mutatis mutandis to the use of the present invention for the above-mentioned production. The following also preferably apply mutatis mutandis to vehicle tires according to the present invention.

[0129] It is preferred for use in the manufacture of any tire components (including outer components and / or inner components), preferably for the manufacture of outer components, and particularly preferably for the manufacture of flange profiles, treads and / or sidewalls. It is particularly preferred for use in the manufacture of caps for treads having a cap / base structure. The type of component is preferably determined by different molding 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 the inner components is typically also called the body mixture. Different components having different shapes and being in an unvulcanized state are typically used for the manufacture of green tires. The unvulcanized green tire is then preferably 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 type of strength member.

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

[0132] Preferably, the compounds according to the present invention described as preferred above are not used as dyes or pigments in pharmaceutical products and electronic devices (particularly preferably displays, particularly OLED displays), respectively.

[0133] Process for producing the compound according to the present invention: The present invention relates to a process for producing a compound according to the present invention, preferably a compound according to formula (I), i) Formula (B1): [ka] Process steps for manufacturing or providing the compound ii) The compound of formula (B1) - Hydrogen and ketones or aldehydes, preferably ketones. And react with equation (I): [ka] (In the formula, - R 1 teeth, - xi) Aromatic group, and - xii) Aliphatic C3~C 12 base Selected from the group consisting of, - R 2 and R 3 They are either the same or different, and aliphatic C1-C 12 A group independently selected from the group consisting of a group, aromatic group, halogen group, cyano group, ester group, ketone group, ether group and thioether group, - R 4 is aliphatic C1-C 20 Groups and aromatic C5~C 20 Selected from a group consisting of elements, - X represents oxygen or sulfur, preferably oxygen. - m is 0, or 1, or 2, or 3. - n is 0, or 1, or 2, or 3, or 4, and - Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, aminos, and nitros, preferably aminos and nitros. Process steps for obtaining the compound Further details regarding the process, including the process itself.

[0134] The foregoing relating to the compounds according to the present invention (preferably and especially as defined above herein as preferred) also preferably apply mutatis mutandis to the manufacturing methods according to the present invention. All the foregoing statements made in connection with the description of the compounds according to the present invention, including preferred embodiments and all levels of priority and possible combinations of these features, are R 1 , R 2 , R 3 , R 4It should be understood that this means it applies to m and n.

[0135] In Z, it is preferable that the halogen is chlorine, bromine, or iodine, preferably chlorine. It is particularly preferable that fluorine is not present.

[0136] In Z, it is preferable that the sulfonate leaving group includes a triflate, nonaflate, mesylate, or tosylate.

[0137] Z is very preferably a nitro or an amine, and particularly preferably a nitro. Therefore, a very preferred starting compound is the corresponding amino or nitro reactant.

[0138] The process according to the present invention is preferred in which the reaction with hydrogen in step ii) is carried out using a catalyst, preferably using a hydrogenation catalyst, as described above and / or below. This means that step ii) preferably uses or employs such a catalyst. Where applicable, “hydrogenation catalyst” is also called “hydrogenation catalyst,” and in relation to the present invention, both terms have the same scope of definition.

[0139] In step ii), the process according to the present invention 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, preferably as described above and / or below. 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.

[0140] A metal, preferably a precious metal, is used 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.

[0141] The process according to the present invention is preferable, wherein the reaction with hydrogen in step ii) takes place over a duration of 1 to 30 hours, preferably 3 to 22 hours, particularly preferably 5 to 16 hours, and most preferably 8 to 13 hours, as described above and / or below.

[0142] The process according to the present invention is preferable, wherein the reaction with hydrogen in step ii) is carried out in a pressurized reactor, preferably in an autoclave, preferably as described above and / or below.

[0143] The reaction in step ii) - This is done using a catalyst, and / or (preferably and) - This 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 especially preferably 85°C to 130°C, and / or (preferably and) - The process according to the present invention is particularly preferred to be carried out at a pressure of 20 to 70 bar, preferably 28 to 57 bar, and especially preferably 35 to 45 bar.

[0144] In the process according to the present invention, the ketone in step ii) is subsequently converted to group 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.

[0145] The process according to the present invention is preferred, wherein the solvent is used in step ii), and the solvent is preferably the same as the ketone / aldehyde or different from (preferably the same as) the ketone / aldehyde, preferably as described above and / or below.

[0146] 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, i.e., not a reactant itself. Preferred inert solvents include toluene, dioxane (preferably 1,4-dioxane), 2-methyltetrahydrofuran (2-MTHF), and / or xylene. This is preferably the case when the aldehyde / ketone is in solid form under the reaction conditions. In the latter case, the ketone / aldehyde is preferably used only as a reactant in the amount stoichiometrically required (a slight excess is sometimes preferred).

[0147] The process according to the present invention 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, preferably as described above and / or below. This makes it possible to omit any additional compounds such as toluene or xylene.

[0148] The process according to the present invention is preferable, preferably as described above and / or below, which involves one or more purification steps, preferably filtration, chromatography, recrystallization and / or washing with a solvent, following step ii). Preferably, a preferred solvent different from the solvent used in step ii) is an alcohol and / or 2-MTHF, preferably methanol and / or ethanol, particularly preferably ethanol. Chromatography including silica gel is preferred. Recrystallization from hydrocarbons, preferably C5-C20 aliphatic compounds, particularly preferably cyclohexane and / or cycloheptane is preferred.

[0149] The present invention will now be described more specifically using exemplary embodiments. [Examples]

[0150] Synthesis of the compound of formula (I): Compound (III), as an exemplary embodiment of compound (I), was prepared by the following steps.

[0151] Step 1 (Synthesis of 5H-phenophosphadinin-10-oxide): 5H-phenophosphadinine-10-oxide was prepared according to M. Haering, Helvetica Chimica Acta, 1960, 43, 1826-1840, and then recrystallized from methanol. This yielded formula (a): [ka] We obtained the compound.

[0152] Stage 2 (10-octyl-5H-phenophosphadinine-10-oxide): In the second step, the 5H-phenophosphadinine-10-oxide obtained in the first step was converted to 10-octyl-5H-phenophosphadinine-10-oxide under protective gas conditions. 1.50 g (6.97 mmol, 1 equivalent) of 5H-phenophosphadinine-10-oxide was dissolved in 30 ml of DMA (dimethylacetamide). 114 mg (0.70 mmol, 0.1 equivalent) of AIBN (azobis(isobutyronitrile)) and 1.54 ml of 1-octene (9.76 mmol, 1.4 equivalents) were added, and the mixture was heated to 85°C and stirred overnight. The solvent was then removed under vacuum. A colorless oil product was obtained in 2.25 g yield (99% of the theoretical yield). Formula (b): [ka] We obtained the compound. 1H-NMR(500MHz,DMSO-d6)δ=10.07(s,1H),7.75(ddd,J=11.9,7.7,1.5Hz,2H),7.51(ddd,J=8.5,7.1,1.5Hz,2H),7.1 5(dd,J=8.3,5.2Hz,2H),7.08(td,J=7.4,1.3Hz,2H),2.09-1.96(m,2H),1.21-0.94(m,12H),0.80(t,J=7.2Hz,3H). 13 C-NMR(126MHz,DMSO-d6)δ=142.6,142.5,132.9,130.8,130.7,120.7,120.6 ,116.4,116.3,112.1,111.3,33.2,31.5,30.2,28.8,25.9,22.5,21.4,14.8. 31 P-NMR (202 MHz, DMSO-d6) δ = 13.7. Mass spectrometry results: ESI-MS[M+H] + = 328.

[0153] In the alternative synthesis, the compound of formula (b) was prepared according to “Chemistry of phosphorus heterocycles”, M. Tajbakhsh-Jadidi, doctoral thesis, Manchester (1980) (the synthesis has not been further clarified).

[0154] Stage 3 (2-nitro-10-octyl-5H-phenophosphadinine-10-oxide): 0.95 g (2.90 mmol) of 10-octyl-5H-phenophosphadinine-10-oxide was dissolved in 20 ml of glacial acetic acid at room temperature. A solution of 2.25 ml of 65% nitric acid and 3.15 ml of glacial acetic acid was added dropwise to this solution at a temperature not exceeding 25°C. This formed an orange solution, which was poured onto ice after 1 hour, thus allowing for subsequent filtration of the solid. Subsequently, the solid was dissolved in DCM (or CHCl3 / n-BuOH 3:1) (with optional addition of triethylamine) and extracted with saturated sodium hydride solution and sodium chloride solution. The solid was dried over sodium sulfate, inorganic components were removed by filtration, and the solvent was removed under vacuum. The obtained solid was purified by crystallization from 2-MeTHF (an alternative attempt was by column chromatography using dichloromethane / methanol, 100:0 → 95:5). This yielded the compound of formula (c). The compound was obtained as a lemon-yellow solid in a yield of 0.8 g (74% of the theoretical yield). [ka] 1 H-NMR(500MHz,DMSO-d6)δ=10.92(s,1H),8.62(dd,J=12.3,2.7Hz,1H),8.33(dd,J=9.2,2.7Hz,1H),7.89-7.81(m,1H),7. 63(t,J=7.7Hz,1H),7.34-7.23(m,3H),2.13(qq,J=14.7,6.8,6.1Hz,2H),1.22-0.97(m,12H),0.80(td,J=7.3,3.2Hz,3H). 13 C-NMR(126MHz,DMSO-d6)δ=147.1,141.1,140.2,133.6,131.0,128.3,128.0,12 3.0,117.5,112.8,112.1,111.4,31.5,30.0,29.9,28.7,28.6,22.5,22.2,14.3. 31 P-NMR(202MHz,DMSO-d6)δ=13.91. Mass spectrometry results: ESI-MS[M+H] + = 373.

[0155] Stage 4 (2-(1,3-dimethylbutylamino)-10-octyl-5H-phenophosphadinine-10-oxide): 163 mg (0.44 mmol) of 2-nitro-10-octyl-5H-phenophosphadinine-10-oxide, 37 mg of platinum-carbon (0.4 g on a 5% 4.67 mmol substrate), and 20.0 ml of methyl isobutyl ketone (MIBK) were weighed into a stainless steel autoclave fitted 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 crystallization from cyclohexane. The resulting purified product was a purplish-brown solid with a yield of 155 mg (83% of the theoretical yield). This yielded the compound of formula (III). 1 H-NMR(500MHz,DMSO-d6)δ=9.66(s,1H),7.67(dd,J=11.9,7.7Hz,1H),7.45-7.39(m,1H),7.05(dd,J=8.4,5.3Hz,1H),6 .96(q,J=7.6Hz,2H),6.85(d,J=29.3Hz,2H),4.27(s,1H),3.09(qd,J=7.3,4.8Hz,1H),1.93(ddd,J=15.1,9.9,5.9Hz,2 H),1.71(dddt,J=19.5,13.1,8.2,6.6Hz,2H),1.45(dtd,J=13.7,7.1,3.1Hz,1H),1.18(td,J=7.2,2.7Hz,2H),1.09(dt ,J=10.2,6.2Hz,8H),0.93(d,J=6.6Hz,3H),0.88(dd,J=6.6,4.9Hz,2H),0.87-0.83(m,6H),0.80(td,J=7.2,1.1Hz,3H). 31 P-NMR(202MHz,DMSO-d6)δ=14.37. Mass spectrometry results: ESI-MS[M+H]+ = 427.

[0156] Further compounds of formula (I): In an alternative synthesis based on “Chemistry of phosphorus heterocycles”, M. Tajbakhsh-Jadidi, doctoral thesis, Manchester (1980), the compound of formula (II) (wherein n and m are zero, R) 1 It is dimethylbutyl, and R 4 (Phenyl) was prepared by a method similar to the procedure described above (the synthesis is not further disclosed).

[0157] 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.

[0158] For this purpose, the compound of formula (III) and 6PPD for comparison were used in both cases, with the polymer (liquid synthetic polyisoprene (IR), LIR-50, Kuraray, weight-average molecular weight distribution M w = 54000 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" as described above in this invention.

[0159] Heating to 180℃: The temperature was started at 35°C, and the mixture was first heated to 170°C at a heating rate of 20 K / min (Kelvin / min), and then further heated to 180°C at a heating rate of 1 K / min (purge gas: nitrogen (N2), volumetric flow rate 50 ml / min).

[0160] 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).

[0161] 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.

[0162] Oxidation was observed using DSC (Differential Scanning Calorimetry). The time (in minutes) until the onset of oxidation was measured in each case. The results, compared with the known aging stabilizer 6PPD, are summarized in Table 1.

[0163] [Table 1]

[0164] Table 1 shows that, particularly at the demanding temperature of 180°C, the compound of formula (III) exhibits a sufficiently good protective effect compared to 6PPD, i.e., approximately 75%. This is also true at 150°C (approximately 71%). Therefore, the potential protective effect should be evaluated as good overall.

[0165] Generally, compounds of formula (I) and especially those of formula (III) are based on the basic structure of phenophosphadinine or phenophosphadinine-10-oxide. In comparison, 6PPD is based on the basic structure of diphenylamine. However, phenophosphadinine derivatives may have lower environmental and health hazards. The compounds / classes of compounds according to the present invention further achieve complete and sufficient protective effects.

[0166] 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.

[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 examples are rubber mixtures that contain 6PPD instead of the compound of formula (III) as an aging stabilizer, but have the same composition otherwise, 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.) without aging stabilizers are also reported.

[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 also show comparable and sufficient aging stabilization effects compared to typical rubber mixtures, particularly those known from the prior art (data not shown). In contrast, the reference shows an overall insufficient aging stabilization effect.

Claims

1. Equation (I): 【Chemistry 1】 (In the formula, - R １ teeth, - xi) Aromatic group, and - xii) aliphatic C ３ ~C １２ base Selected from the group consisting of, - R ２ and R ３ are either the same or different, and aliphatic C １ ~C １２ A group independently selected from the group consisting of a group, aromatic group, halogen group, cyano group, ester group, ketone group, ether group and thioether group, -R ４ is selected from the group consisting of aliphatic C １ to C ２０ groups and aromatic C ５ to C ２０ groups, - X represents oxygen or sulfur, - m is 0, or 1, or 2, or 3, and (n is 0, 1, 2, 3, or 4) A compound of [this].

2. Formula (II): 【Chemistry 2】 (In the formula, R １ , R ２ , R ３ , R ４ (X, m, and n are as defined in claim 1) The compound according to claim 1, having the structure.

3. The compound according to claim 1 or 2, wherein n and m are the same or different, preferably the same.

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

5. R ４ is aromatic C ５ ~C １８ A group, preferably an aromatic compound C ５ ~C １６ more preferably aromatic C ５ ~C １４ A group, particularly preferably an aromatic C ６ ~C １２ The base, and most preferably aromatic C ６ ~C １０ A compound according to any one of claims 1 to 4, which is a base.

6. R ４ is aliphatic C １ ~C １８ Base, preferably aliphatic C ２ ~C １６ Base, more preferably aliphatic C ３ ~C １４ A base, particularly preferably an aliphatic C ４ ~C １２ As a base, and especially preferably aliphatic C ５ ~C １０ A compound according to any one of claims 1 to 4, which is a base.

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

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

9. Formula (III): 【Transformation 3】 A compound according to any one of claims 1 to 8, having the structure of the compound.

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. Preferably, - Vehicle tires, especially preferably pneumatic vehicle tires, - Particularly preferred are rubber articles different from vehicle tires, 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 robotics applications, soles and parts of soles. - Oil and / or grease, and / or - Fuel and / or lubricant Use of the compound according to any one of claims 1 to 9 as an anti-aging stabilizer and / or antioxidant in the context of

13. - Vehicle tires, preferably pneumatic vehicle tires, and / or - Particularly preferred are rubber articles different from vehicle tires, 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 robotics applications, shoe soles and parts of shoe soles. Use of the rubber mixture according to claim 10 for manufacturing the product.

14. A process for producing the compound of formula (I), i) Formula (B1): 【Chemistry 4】 Process steps for manufacturing or providing the compound ii) The compound of formula (B1) above, - Hydrogen and ketones or aldehydes, preferably ketones Reacting with the above equation (I): 【Transformation 5】 (In the formula, - R １ teeth, - xi) Aromatic group, and - xii) aliphatic C ３ ~C １２ base Selected from the group consisting of, - R ２ and R ３ are either the same or different, and aliphatic C １ ~C １２ A group independently selected from the group consisting of a group, aromatic group, halogen group, cyano group, ester group, ketone group, ether group and thioether group, - R ４ is aliphatic C １ ~C ２０ groups and aromatic C ５ ~C ２０ Selected from a group consisting of elements, - X represents oxygen or sulfur, - m is 0, or 1, or 2, or 3. - n is 0, or 1, or 2, or 3, or 4, and - Z is selected from the group consisting of halogens, sulfonates, sulfonate-based leaving groups, aminos, and nitros, preferably aminos and nitros. Process steps for obtaining the compound A process that includes this.

15. The reaction in step ii) is - 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 especially preferably 85°C to 130°C, and / or - The process according to claim 14, carried out at a pressure of 20 to 70 bar, preferably 28 to 57 bar, and particularly preferably 35 to 45 bar.

Images