Compounds, rubber blends containing the compounds, vehicle tires comprising at least one component of the rubber blends, processes for preparing the compounds, and use of the compounds as anti-aging and / or antioxidant agents

Abstract

The present invention relates to a compound, 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 antiaging agent and / or antioxidant. The compound according to the present invention has the formula (I): TIFF2025512926000022.tif22170 (in the formula, R 1 xi) aromatic groups optionally having a substituent selected from the group consisting of halogen, cyano, ester, ketone, ether and thioether groups, and xii) linear, branched and cyclic aliphatic C3-C 12 wherein the aryl group is selected from the group consisting of

Description

[Technical field]

[0001] The present invention relates to the compounds, to rubber mixtures containing the compounds, to vehicle tires comprising the rubber compound in at least one component, to a process for the manufacture of the compounds, and to the use of the compounds as ageing stabilizers and / or antioxidants. [Background technology]

[0002] Polymeric materials, particularly rubber, are known for use in vehicle tires and industrial rubber articles.

[0003] In case of long-term storage and especially in the intended use, which is often at high temperatures, natural rubber and synthetic polymers (such as IR, BR, SSBR, ESBR, etc.), as well as natural and synthetic oils, fats and lubricants, undergo oxidation reactions that adversely affect their original desired properties. Depending on the type of polymer, the polymer chains shorten until the material liquefies or the material then hardens.

[0004] Thus, aging stabilizers contribute significantly to the service life of vehicle tires and other industrial rubber articles.

[0005] Known aging stabilizers include aromatic amines, e.g. 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) is included.

[0006] These molecules are capable of reacting with oxygen or ozone, or with free radicals that are formed, such as alkyl, alkoxy and alkylperoxy groups, thus scavenging them, thereby protecting the polymer from further oxidation reactions. Summary of the Invention [Problem to be solved by the invention]

[0007] However, a drawback of this substance class is that they may be carcinogenic.

[0008] Antioxidants that specifically react with ozone and result in its scavenging are also called "antiozonants."

[0009] A further problem associated with aging stabilizers is the undesirable blooming. Here, due to the rather poor solubility of the molecules of the aging stabilizer in the polymer matrix surrounding the rubber article, they diffuse to the surface of the article to be protected, causing the formation there of a film that is usually distinguishable in color from the rest of the article. In the case of vehicle tires, this is usually manifested as a brown coloration of the otherwise black sidewall. In addition to the aesthetic disadvantage, this is also associated with a disadvantage in terms of the aging stabilization effect. For this reason, the bloomed material is usually removed. This firstly reduces the total amount of aging stabilizer and also affects the diffusion of further molecules of aging stabilizer to its location, resulting in a lower level of protection of the polymer. [Means for solving the problem]

[0010] The aim of the present invention is to provide new compounds which can be used in particular as ageing stabilizers for vehicle tyres or other industrial rubber articles, and which in particular have a lower potential hazard, in combination with a sufficient solubility in the respective matrix, for example in particular in polymers, which are intended to prevent the tendency to blooming whilst maintaining an optimal protection against oxygen and ozone, reducing the hazards to health.

[0011] At the same time, the compounds are intended to ensure comparable or even improved aging stabilization compared to aromatic amines such as 6PPD.

[0012] This object is achieved by the compound according to the invention as claimed in claim 1, by rubber mixtures according to the invention which contain said compound, and by vehicle tyres according to the invention which comprise in at least one component thereof a rubber mixture according to the invention.

[0013] This object is also achieved by the process according to the invention for the preparation of the compounds according to the invention.

[0014] The compound of claim 1 has the general formula I: [ka] In the formula, R 1 xi) an aromatic group optionally having a substituent selected from the group consisting of a halogen group, a cyano group, an ester group, a ketone group, an ether group and a thioether group; and xii) linear, branched and cyclic aliphatic C3-C 12 is selected from the group consisting of base R 2 and R 3 may be the same or different, independently of one another, and are linear, branched and cyclic, saturated and unsaturated, aliphatic C1-C cyclic alkyl groups, optionally bearing one or more halogen substituents. 12 groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups, with fluorine, bromine and chlorine being preferred, cyano groups, ester groups, ketone groups, ether groups and thioether groups; m takes the value 0, 1, 2, or 3; n is an integer of 0 or 1 to 8, preferably 1 to 4.

[0015] For example, when m is 0 (zero) or 1 or 2, each hydrogen atom is represented by R 2 It will be apparent to those skilled in the art that instead of R 3 and similarly applies to n less than 8.

[0016] Similarly, for each ring of the structure, (R 2 ) m and (R 3 ) n and R 1It will be apparent to one of skill in the art that the HN bond representation means that these groups may each be located at any position on the respective ring, while observing the tetravalency of the carbon atom.

[0017] In relation to the present invention, "C3-C 12 The reference to "a group" is understood to mean a group having 3 to 12 carbon atoms. Regardless, "C1" is used to represent the position of the most highly oxidized carbon atom / highest priority carbon atom according to the Cahn-Ingold-Prelog rule (CIP). What is meant in each case will be clear to those skilled in the art.

[0018] The compounds according to the invention are tetrahydrocarbazole derivatives and exhibit a lower hazard potential compared to known aging stabilizers based on aniline (possible cleavage products of 6PPD).

[0019] This is a very important advantage, especially in industrial applications such as vehicle tires or other rubber products, where rubber components can become dislodged through wear or other degradation processes.

[0020] Compared to the known ageing stabilizer 6PPD, the compounds according to the invention show comparable or even improved antioxidant effects, so that the compounds of formula I) achieve comparable or even improved protective effects, in particular in vehicle tyres and other industrial rubber articles, but also in oils and lubricants.

[0021] However, the present invention is not bound to any particular mechanism of action or to any particular explanation.

[0022] The compounds according to the invention are therefore suitable as alternatives to 6PPD, the degradation products of which are highly toxic to Coho salmon and therefore possibly also to other aquatic organisms.

[0023] The compound according to the present invention further has very good solubility in rubber mixtures, especially in vehicle tires and other industrial rubber articles.This means that the blooming of this compound, which often occurs with many aging stabilizers, is avoided, which means that the aging stabilization effect is advantageous / improved.The less the bloom of the aging stabilizer, the less the aging stabilizer is intentionally or unintentionally removed from the surface of the article to be protected, and as a result, the less the aging stabilizer diffuses to the surface.

[0024] The compounds of formula I) according to the invention are particularly suitable as ageing stabilizers and / or antiozonants in vehicle tyres and / or other industrial rubber articles, such as, in particular, air springs, bellows, conveyor belts, straps, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical or robotic use or shoe soles or parts thereof, and / or in oils and / or lubricants.

[0025] The compounds of formula I) according to the invention are particularly suitable for the manufacture of rubber articles, in particular air springs, bellows, conveyor belts, straps, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical or robotic use or shoe soles or parts thereof.

[0026] For the use of the compounds of formula I) in the recited articles or materials, said compounds are used in compositions and are used incorporated into said compositions.

[0027] In vehicle tires or other industrial rubber articles, said composition is especially a rubber mixture.

[0028] The present invention further provides the use of the compounds of formula I) according to the invention in oils and lubricants, in particular engine fuels or fluids, etc. In particular, the compounds according to the invention can be used in engines. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] The present invention includes all advantageous embodiments, in particular those reflected in the claims. The present invention also includes embodiments resulting from combinations of different features having different priorities relative to these features, in particular so that the invention also includes combinations of a first feature described as "preferred" or in the context of an advantageous embodiment with a further feature, for example described as "particularly preferred".

[0030] Furthermore, all information concerning the characteristics of the compounds according to the invention also applies to the processes according to the invention for preparing the compounds and to the rubber mixtures according to the invention containing the compounds and to the uses according to the invention.

[0031] -N(H)R 1 The group is preferably positioned para to the N(H).

[0032] Thus, the compound according to the invention preferably has the formula II: [ka] wherein R 1 , R 2 , R 3 and m and n are as defined above.

[0033] This achieves the object of the invention particularly well and in particular achieves very good solubility of the compounds in rubber mixtures, in particular vehicle tyres.

[0034] base R 2 and R 3 are each independently the same or different, and are linear, branched and cyclic, saturated and unsaturated, aliphatic C1-C 12 groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups (wherein fluorine, bromine and chlorine are preferred), cyano groups, ester groups, ketone groups, ether groups and thioether groups.

[0035] The enumerated groups R 2and R 3 may in particular already be attached to the respective ring / its precursor by the selection of suitable starting materials.

[0036] The tetravalency of the carbon means that m can have a maximum value of 3. Thus, up to three substituents R 2 may be attached to the benzene ring.

[0037] The tetravalency of carbon means that n can have a maximum value of 8. Thus, up to eight substituents R 3 may be attached to the cyclohexene ring.

[0038] However, in a preferred embodiment, n is an integer from 1 to 4, and each carbon atom preferably has one group R 3 Only has.

[0039] This makes the molecule more stable due to less steric congestion. Synthetically easy-to-obtain precursors contain a benzene ring and therefore up to four groups R instead of the cyclohexyl ring. 3 Since only one n can be introduced, compounds in which n is 0 or 1 to 4 are even easier to synthesize.

[0040] For example, it is particularly preferred, particularly in formulae I) and II), that m is zero (0).

[0041] For example, it is particularly preferred, particularly in formulae I) and II), that n is zero (0).

[0042] This results in a compound of formula Ia) or IIa): [ka] In the formula, R 1 is as defined above.

[0043] base R 1 teeth, xi) an aromatic group optionally having a substituent selected from the group consisting of a halogen group, a cyano group, an ester group, a ketone group, an ether group, and a thioether group; and xii) linear, branched and cyclic aliphatic C3-C 12 The group consisting of:

[0044] The aromatic groups of subgroup xi) are, for example, preferably selected from the phenyl group (-C6H5) and the benzyl group (-CH2-C6H5), with phenyl being particularly preferred.

[0045] The aromatic groups of subgroup xi) may optionally contain substituents.

[0046] As mentioned above, these are selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups.

[0047] It is preferred if the substituents are selected from the group consisting of ester groups, ketone groups, ether groups and thioether groups.

[0048] In a preferred embodiment, the aromatic group is not substituted at the two carbon atoms adjacent to the C1 atom, i.e., the carbon atom bonded to the N atom. Thus, in the case of a benzene ring as a basic structure, it is preferred that there is no substituent at the ortho position relative to the N atom.

[0049] In a further preferred embodiment the aromatic radicals of subgroup xi) are unsubstituted.

[0050] R 1 is preferably linked to the nitrogen atom (N) via a tertiary carbon atom, i.e., the C1 atom is preferably a tertiary carbon atom.

[0051] In the context of the present invention, the term "tertiary carbon atom" is understood to mean a carbon atom which is bonded to only one hydrogen atom.

[0052] This, compared to secondary and quaternary carbon atoms, results in a particularly good protective effect due to the presence of the compound in rubber mixtures, especially vehicle tires and other industrial rubber articles, and leads to optimal reactivity, especially in relation to mechanisms related to ageing stabilization, avoiding undesirable side reactions.

[0053] In a further advantageous embodiment, in particular in the above formulae I), II), Ia) and IIa), R 1 is a branched or cyclic alkyl group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, where R 1 is particularly preferably selected from the 1,3-dimethylbutyl and cyclohexyl radicals, where R 1 is very particularly preferably the 1,3-dimethylbutyl group.

[0054] This achieves particularly good solubility in rubber mixtures for vehicle tires and other industrial rubber articles.

[0055] In a particularly preferred embodiment, the compound according to the invention has formula III: [ka] It has the structure:

[0056] The compounds of formula III) have particularly good solubility in polymers, especially in rubber mixtures for vehicle tires and other industrial rubber articles. At the same time, the compounds of formula II) can be produced in a particularly simple, energy-efficient and cost-saving manner and show comparable or even improved antioxidant effect and therefore comparable or improved aging stabilization effect compared to 6PPD.

[0057] According to the IPUAC nomenclature, the compound of formula III) can also be called 6-(1,3-dimethylbutylamino)-2,3,4,9-tetrahydro-1H-carbazole.

[0058] As mentioned above, the present invention further provides a method for preparing a compound of formula I), comprising at least the following process steps: i) producing or providing a substance of formula B1): [ka] ii) reacting the compound of formula B1) with hydrogen and a ketone or aldehyde, preferably a ketone, to obtain the compound of formula I): [ka] In the formula, R 1 xi) an aromatic group optionally having a substituent selected from the group consisting of a halogen group, a cyano group, an ester group, a ketone group, an ether group and a thioether group; and xii) linear, branched and cyclic aliphatic C3-C 12 is selected from the group consisting of base R 2 and R 3 may be the same or different, independently of one another, and are linear, branched and cyclic, saturated and unsaturated, aliphatic C1-C cyclic alkyl groups, optionally bearing one or more halogen substituents. 12 groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups, with fluorine, bromine and chlorine being preferred, cyano groups, ester groups, ketone groups, ether groups and thioether groups; m takes the value 0, 1, 2, or 3; n is an integer of 0 or 1 to 8, preferably 1 to 4.

[0059] All of the above information provided in connection with the description of compounds according to the invention, including preferred embodiments, and taking into account any possible hierarchy of preferences for these features and combinations of these features, is incorporated herein by reference in its entirety. 1 , R 2 , R 3 , m and n.

[0060] Compounds of formula B1) can be prepared, for example, according to BADalvi, Tet. Lett., 2018, 59, 2145-2149, as well as according to the following scheme S1): [ka] where AcOH represents acetic acid.

[0061] All the above information is provided by R 1 , R 2 , R 3 , m and n, where in the cyclohexanone derivatives, one of the carbon atoms adjacent to the carbonyl group is a group R 3 In Scheme S1), this carbon atom is characterized by being explicitly shown as having two hydrogen atoms attached.

[0062] The group -N(H)R in formula I 1 and the group --NO.sub.2 in starting material B1) is preferably located in the para position relative to the N(H) and N(H)--N(H)2, respectively, as described above.

[0063] Thus, the compounds prepared according to the present invention preferably have the formula II: [ka] It has the structure:

[0064] For this purpose, the starting material of formula B1) is preferably of formula B1a): [ka] wherein R 1 , R 2 , R 3 and m and n are as defined above, including all embodiments and combinations of features.

[0065] It is preferred if the reaction with hydrogen in step ii) uses a suitable catalyst, which in the context of the present invention is referred to as a "hydrogenation catalyst".

[0066] The hydrogenation catalyst is preferably a noble metal catalyst, in particular palladium (Pd) or platinum (Pt). Noble metals are preferably used on carbon (C), such as palladium on carbon (Pd / C).

[0067] Additionally, other known catalysts such as Raney nickel or copper chromite may also be used.

[0068] Therefore, it is particularly preferred that the reaction of step ii) is carried out using a hydrogenation catalyst.

[0069] The reaction in step ii) is preferably carried out at a temperature of 50°C to 130°C, preferably 50°C to 100°C, particularly preferably 50°C to 80°C, in particular 60°C for example.

[0070] It is preferred if the reaction mixture is subjected to hydrogen at a pressure of 10 to 70 bar, particularly preferably 10 to 30 bar, in particular for example 20 bar, and then preferably stirred for 1 to 20 hours, preferably for 3 to 13 hours, particularly preferably for 5 to 13 hours, in particular for example for 10 hours.

[0071] The reaction with hydrogen in step ii) is preferably carried out in a vessel suitable for relatively high pressures, such as in particular in an autoclave or another pressure reactor.

[0072] Particular preference is given to the case where the reaction of step ii) is carried out with hydrogen using a hydrogenation catalyst at temperatures between 50° C. and 130° C., preferably between 50° C. and 100° C., particularly preferably between 50° C. and 80° C., and the reaction mixture is subjected to hydrogen at a pressure of, for example, between 10 and 70 bar, particularly preferably between 10 and 30 bar, in particular 20 bar, and the reaction is carried out in an autoclave or a separate pressure reactor.

[0073] In step ii) the ketone is reacted with the subsequent group R 1 in the case of an aldehyde it is therefore an aldehyde derivative.

[0074] For simplicity, the group R 1 is the moiety remaining on the nitrogen atom after reaction with an aldehyde or ketone, hence the abbreviated formula R 1 =O is used for aldehydes or ketones.

[0075] The ketone used here is preferably methyl isobutyl ketone.

[0076] The solvent in step ii) can be either the ketone or aldehyde, if it is in liquid form, or an inert solvent, such as toluene or xylene, especially if the ketone or aldehyde is in solid form. In the latter case, the ketone or aldehyde is used only as reactant in stoichiometric amounts.

[0077] A ketone or aldehyde in liquid form as a solvent R 1 It is preferred to use =O, particularly preferably a ketone, which makes it possible to omit any additional substances such as toluene or xylene.

[0078] Step ii) is preferably followed by purification, e.g. by filtration and scrubbing with a solvent, in particular ethanol, and / or by column chromatography, e.g. on silica gel, or by recrystallization from cyclohexane or long chain aliphatics.

[0079] As mentioned above, the present invention further provides a rubber mixture.

[0080] The rubber mixtures according to the invention contain, for example, compounds of formula I), preferably compounds of formula III. The rubber mixtures according to the invention may in principle be any rubber mixture in which, in particular, the novel compounds of formula I) or III) according to the invention act as ageing stabilizers and / or antiozonants with low toxicity.

[0081] The rubber mixture according to the invention contains at least one rubber.

[0082] It is preferred if the rubber mixture according to the invention contains 0.1 to 10 phr, particularly preferably 0.1 to 7 phr, very particularly preferably 1 to 6 phr, next preferably 1 to 3 phr of compounds of the formula I), for example preferably compounds of the formula III).

[0083] The rubber mixture may also comprise a mixture of two or more compounds complying with formula I).

[0084] The unit "phr" (parts per hundred parts by weight of rubber) used in this document is the customary designation of quantities for mixture formulations in the rubber industry. The dosage of parts by weight of an individual substance is herein defined as the total amount of high molecular weight (M w The standard is based on 100 parts by weight of the total mass of rubber (whose molecular weight exceeds 20,000 g / mol).

[0085] In an advantageous embodiment of the invention, the inventive rubber mixture contains at least one diene rubber.

[0086] Thus, the rubber mixture may contain a diene rubber or a mixture of two or more different diene rubbers.

[0087] Diene rubbers are rubbers formed by the polymerization or copolymerization of dienes and / or cycloalkenes and therefore have C=C double bonds either in the backbone or in side groups.

[0088] The diene rubber is preferably 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, molecular weight M wis selected from the group consisting of liquid rubber having a molecular weight greater than 20,000 g / mol, halobutyl rubber, polynorbornene, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber, nitrile rubber, chloroprene rubber, acrylate rubber, fluororubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-butadiene terpolymer, hydrogenated acrylonitrile butadiene rubber, and hydrogenated styrene-butadiene rubber.

[0089] Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber and / or ethylene-propylene-diene rubber are used in particular for the manufacture of industrial rubber articles such as straps, drive belts and hoses and / or shoe soles. Mixture compositions known to those skilled in the art for these rubbers, specific in terms of fillers, plasticizers, vulcanization systems and additives, are preferably used.

[0090] The natural and / or synthetic polyisoprene of all embodiments may be cis-1,4-polyisoprene or 3,4-polyisoprene. However, it is preferred to use cis-1,4-polyisoprene with a cis-1,4 ratio of more than 90% by weight. Firstly, such polyisoprene is accessible by stereospecific polymerization in solution with Ziegler-Natta catalyst or with fine lithium alkyl. Secondly, natural rubber (NR) is such cis-1,4-polyisoprene, in which the cis-1,4 content in natural rubber is more than 99% by weight.

[0091] Mixtures of one or more natural polyisoprenes and one or more synthetic polyisoprenes are further contemplated.

[0092] In the context of the present invention, the term "natural rubber" should be understood to mean natural rubber obtainable from the Hevea rubber tree, as well as from "non-Hevea" sources, such as the guayule shrub and dandelions, such as TKS (Taraxacum kok-saghyz).

[0093] If the rubber mixture of the present invention contains butadiene rubber (i.e. BR, polybutadiene), this may be of any type known to those skilled in the art. These include those called high-cis and low-cis types, where polybutadienes with a cis content of 90% or more by weight are called high-cis types and polybutadienes with a cis content of less than 90% by weight are called low-cis types. An example of a low-cis polybutadiene is Li-BR (lithium catalyzed butadiene rubber) with a cis content of 20% to 50% by weight. With high-cis BR, particularly good properties and low hysteresis are achieved in the rubber mixture.

[0094] The polybutadiene used may be end-modified with modifications and functionalizations and / or functionalized along the polymer chain. The modifications may be selected from modifications with hydroxyl groups and / or ethoxy groups and / or epoxy groups and / or siloxane groups and / or amino groups and / or aminosiloxane and / or carboxyl groups and / or phthalocyanine groups and / or silane-sulfide groups. However, further modifications known to those skilled in the art, also called functionalizations, are also useful. Metal atoms may be constituents of such functionalizations.

[0095] If at least one styrene-butadiene rubber (styrene-butadiene copolymer) is present in the rubber mixture, it may be a solution polymerized styrene-butadiene rubber (SSBR) and an emulsion polymerized styrene-butadiene rubber (ESBR), and it is also possible to utilize a mixture of at least one SSBR and at least one ESBR. The terms "styrene-butadiene rubber" and "styrene-butadiene copolymer" are used synonymously in the context of the present invention.

[0096] The styrene-butadiene copolymers employed may be end-group-modified and / or functionalized along the polymer chain by the modifications and functionalizations mentioned above for polybutadiene.

[0097] The at least one diene rubber is preferably selected from the group consisting of natural polyisoprene (NR, natural rubber), synthetic polyisoprene (IR), butadiene rubber (BR), solution polymerized styrene-butadiene rubber (SSBR), emulsion polymerized styrene-butadiene rubber (ESBR), butyl rubber (IIR) and halobutyl rubber.

[0098] In a particularly preferred embodiment of the present invention, the at least one 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).

[0099] In a particularly advantageous embodiment of the invention, the rubber mixture comprises at least one natural polyisoprene (NR), preferably in an amount of 50 to 100 phr, in one particularly advantageous embodiment of the invention in an amount of 80 to 100 phr, more preferably 95 to 100 phr, then preferably 100 phr. Such rubber mixtures exhibit optimized tear and wear properties combined with particularly good processability and reversion stability.

[0100] If the rubber mixture contains less than 100 phr of NR, it preferably contains as further rubber at least one diene rubber 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).

[0101] In a further particularly advantageous embodiment of the invention, the rubber mixture comprises at least one natural polyisoprene (NR), preferably in an amount of 5 to 55 phr, in one particularly advantageous embodiment of the invention in an amount of 5 to 25 phr, more preferably in an amount of 5 to 20 phr. Such rubber mixtures exhibit particularly good processability and recovery stability, as well as optimized tear properties and optimal rolling resistance properties.

[0102] In a further particularly advantageous embodiment of the invention, the rubber mixture comprises at least one polybutadiene (BR, butadiene rubber), preferably in an amount of 10 to 80 phr, more preferably 10 to 50 phr, and in a particularly advantageous embodiment of the invention in an amount of 15 to 40 phr, whereby particularly good tear and wear properties as well as optimal braking properties of the rubber mixture according to the invention are achieved.

[0103] In a further particularly advantageous embodiment of the present invention, the rubber mixture comprises at least one solution polymerized styrene-butadiene rubber (SSBR), preferably in an amount of 10 to 80 phr, more preferably 30 to 80 phr, and in one particularly advantageous embodiment of the present invention in an amount of 50 to 70 phr. This achieves particularly good rolling resistance properties of the rubber mixture of the present invention. In a particularly advantageous embodiment of the present invention, the SSBR is used in combination with at least one further rubber in order to achieve an optimal and balanced property profile.

[0104] It is preferred if the rubber mixture contains at least one filler, preferably in an amount of 30 to 500 phr, more preferably 50 to 400 phr, then preferably in an amount of 80 to 300 phr.

[0105] In an advantageous embodiment of the invention, the filler is a reinforcing filler, preferably selected from the group consisting of carbon black and silicon dioxide.

[0106] Suitable carbon blacks include all kinds of carbon black types known to those skilled in the art. It is preferred if the carbon black is selected from technical carbon black and pyrolytic carbon black, with technical carbon black being more preferred.

[0107] It is preferred that the carbon black has an iodine number according to ASTM D1510, also known as iodine adsorption, of 30 to 250 g / kg, preferably 30 to 180 g / kg, more preferably 40 to 180 g / kg, and even more preferably 40 to 130 g / kg, and a DBP value according to ASTM D2414 of 30 to 200 ml / 100 g, preferably 70 to 200 ml / 100 g, and more preferably 90 to 200 ml / 100 g.

[0108] The DBP value according to ASTM D2414 determines the specific absorption volume of dibutyl phthalate in carbon black or light colored fillers.

[0109] The use of such types of carbon black in rubber mixtures, particularly for vehicle tires, ensures an optimal compromise between wear resistance and heat storage, which in turn affects the ecologically relevant rolling resistance.

[0110] Particularly suitable and preferred carbon blacks are those having an iodine adsorption number of 80 to 110 g / kg and a DBP number of 100 to 130 ml / 100 g, such as, in particular, carbon blacks of the N339 type.

[0111] The silicon dioxide is preferably amorphous silicon dioxide, for example precipitated silica, also called precipitated silicon dioxide. However, it is also possible to use, for example, finely divided silicon dioxide, instead.

[0112] However, 35 to 400 m 2 / g, preferably 35 to 350m 2 / g, more preferably 85 to 320 m 2 / g, and even more preferably 120 to 235 m 2 / g nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) and 30-400 m 2 / g, preferably 30 to 330m 2 / g, more preferably 80 to 300m 2 / g, and even more preferably 115 to 200 m 2 It is particularly preferred to use finely divided precipitated silicas having a CTAB surface area (according to ASTM D 3765) of 100 / g. Such silicas result in particularly good physical properties of the vulcanized rubber, for example in rubber mixtures for tire treads. Advantages in the processing of the mixtures due to reduced mixing times can also be obtained while maintaining the same product properties, resulting in improved productivity. The silicas used can therefore be, for example, Ultrasil® VN3 type (trade name) from Evonik, or highly disperse silicas known as HD silicas (for example Zeosil® 1165 MP from Solvay).

[0113] In a particularly advantageous embodiment of the invention, the rubber mixture contains at least one silica as filler, preferably in an amount of 30 to 500 phr, more preferably 50 to 400 phr, then preferably 80 to 300 phr.

[0114] In these amounts, silica is especially present as the sole or predominant filler (greater than 50% by weight, based on the total amount of filler).

[0115] In a further advantageous embodiment of the invention, the rubber mixture contains at least one silica as further filler, preferably in an amount of from 5 to 100 phr, more preferably from 5 to 80 phr, then preferably from 10 to 60 phr.

[0116] In these amounts, the silica is particularly present as an additional filler, especially in addition to other primary fillers such as carbon black.

[0117] The terms "silicic acid" and "silica" are used interchangeably in the context of the present invention.

[0118] In a particularly advantageous embodiment of the invention, the rubber mixture according to the invention contains from 0.1 to 60 phr, preferably from 3 to 40 phr, particularly preferably from 5 to 30 phr and very particularly preferably from 5 to 15 phr of at least one carbon black. In these amounts, the carbon black is present as a further filler, in particular in addition to the main filler such as silica.

[0119] In a further advantageous embodiment of the invention, the rubber mixture according to the invention contains from 30 to 300 phr, preferably from 30 to 200 phr, particularly preferably from 40 to 100 phr, of at least one carbon black, in these amounts being present alone or as the main filler, and therefore optionally in combination with silica in the amounts towards the lower limits mentioned above.

[0120] In a particularly advantageous embodiment of the invention, the rubber mixture contains from 5 to 60 phr, more preferably from 5 to 40 phr, of at least one carbon black and from 50 to 300 phr, preferably from 80 to 200 phr, of at least one silica.

[0121] The rubber mixture may further contain further reinforcing or non-reinforcing fillers.

[0122] The further (non-reinforcing) fillers, in the context of the present invention, include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide or rubber gels, and fibres (e.g. aramid fibres, glass fibres, carbon fibres, cellulose fibres).

[0123] Further optional reinforcing fillers include, for example, carbon nanotubes (CNTs), such as discrete CNTs, hollow carbon fibers (HCFs) and modified CNTs containing one or more functional groups, such as hydroxy, carboxy and carbonyl groups, graphite and graphene, and what are known as "carbon-silica dual phase fillers."

[0124] In the context of the present invention, zinc oxide is not included in the filler.

[0125] The rubber mixture may further contain conventional additives in conventional parts by weight, which are preferably added in at least one primary mixing stage during the preparation of said mixture. These additives include: a) ageing stabilizers known in the art, For example, p-phenylenediamines, such as 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), or dihydroquinolines, such as 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), b) activators, such as zinc oxide and fatty acids (e.g. stearic acid) and / or other activators, such as zinc complexes, such as zinc ethylhexanoate; c) activators and / or agents for binding fillers, especially carbon black or silica, such as S-(3-aminopropyl)thiosulfate and / or its metal salts (binding of carbon black) and silane coupling agents (binding to silicon dioxide, especially silica); d) antiozonant waxes; e) resins, especially tackifying resins; f) mastication aids, such as 2,2'-dibenzamidodiphenyl disulfide (DBD); g) processing aids, in particular fatty acid esters and metal soaps, for example zinc soaps and / or calcium soaps; h) plasticizers, for example in particular aromatic, naphthenic or paraffinic mineral oil plasticizers, for example MES (Mild Extraction Solvates), preferably having a content of polycyclic aromatic compounds of less than 3% by weight according to method IP 346, or RAE (Residual Aromatic Extract), or TDAE (Processed Distillate Aromatic Extract), or Rubber to Liquid (RTL) oils or Biomass to Liquid (BTL) oils, or triglycerides, for example rapeseed oil or factice, or hydrocarbon resins or liquid polymers with an average molecular weight (determined by GPC = Gel Permeation Chromatography in accordance with BS ISO 11344:2004) of 500 to 20 000 g / mol.

[0126] If a 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 (light extract solvate), and naphthenic oils.

[0127] In a particularly advantageous embodiment, the rubber mixture according to the invention does not contain, in addition to the inventive compound of formula I), for example of formula III), an ageing stabilizer from the group of p-phenylenediamines, in particular those listed above under a). In a particularly preferred embodiment, the rubber mixture according to the invention contains 0 to 0.1 phr, in particular 0 phr, based on p-phenylenediamine, of a further ageing stabilizer, which is selected from the group comprising, preferably consisting of, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine (SPPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD).

[0128] The very small amounts of p-phenylenediamine, preferably 0-0.1 phr, particularly preferably 0 phr, present according to the invention as well as the compounds of formula I), for example formula III), make it possible to achieve the same protective effect with lower toxicity.The compounds of the invention of formula I), for example formula III), replace the listed p-phenylenediamines known in the prior art.

[0129] In a further advantageous embodiment of the present invention, since at least one further representative of the mentioned p-phenylenediamine aging stabilizers is present, the compounds of the present invention only partially replace the p-phenylenediamines known in the prior art, which also achieves the advantages of the present invention, but only to a less than optimal extent.

[0130] In an advantageous embodiment, an ageing stabilizer of the dihydroquinoline type, such as TMQ, is present in the rubber mixture in addition to the compound of formula I) according to the invention. The amount of dihydroquinoline, in particular TMQ, present is preferably from 0.1 to 3, in particular from 0.5 to 1.5 phr.

[0131] The antiozonant waxes (group d above) are considered separately and, in a preferred embodiment of the invention, are present in the rubber mixture regardless of whether or not additional ageing stabilizers a) are present.

[0132] The silane coupling agent can be of any type known to those skilled in the art.

[0133] Additionally, one or more different silane coupling agents may be used in combination with one another, so that a rubber mixture may contain a mixture of different silanes.

[0134] Silane coupling agents react with surface silanol groups or other polar groups of silicon dioxide, especially silica, during mixing of the rubber / rubber mixture (in situ) or in pretreatment (pre-modification) situations, even before the addition of the filler to the rubber.

[0135] Coupling agents known from the prior art are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group as leaving group on the silicon atom and other functional groups which, possibly after cleavage, are capable of entering into a chemical reaction with the double bonds of the polymer. The latter groups may include, for example, the following chemical groups: -SCN, -SH, -NH2 or -S x -(where x=2~8).

[0136] Usable silane coupling agents are thus, for example, 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane or 3,3'-bis(triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms, such as 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT), the corresponding disulfides (TESPD) or other mixtures of sulfides having 1 to 8 sulfur atoms with different sulfides. TESPT can also be added, for example, as a mixture with industrial carbon black (trade name X50S®, manufactured by Evonik).

[0137] Blocked mercaptosilanes, such as known from WO 99 / 09036, can also be used as silane coupling agents. It is also possible to use silanes described in WO 2008 / 083241A1, WO 2008 / 083242A1, WO 2008 / 083243A1 and WO 2008 / 083244A1. Usable silanes include, for example, 3-octanoylthio-1-propyltriethoxysilane, which is sold in many varieties by Momentive in the United States under the name NXT, or sold by Evonik Industries under the name VP Si 363®.

[0138] The total proportion of further additives is preferably between 3 and 150 phr, more preferably between 3 and 100 phr, most preferably between 5 and 80 phr.

[0139] Zinc oxide (ZnO) may be included in the overall proportion of further additives in the amounts mentioned above.

[0140] This can be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder. The zinc oxide commonly used is generally 10 ml 2 / g. However, it has a BET surface area of ​​10 to 100 m 2 It is also possible to use zinc oxide having a BET surface area of ​​100 nm / g, for example "nano zinc oxide".

[0141] The rubber mixtures of the invention are preferably used in vulcanized form, in particular in vehicle tyres or other vulcanization technical rubber articles.

[0142] The terms "vulcanization" and "crosslinking" are used synonymously in the context of the present invention.

[0143] The vulcanization of the rubber mixture of the present invention is preferably carried out in the presence of sulfur and / or sulfur donors with the aid of vulcanization accelerators, some of which can simultaneously act as sulfur donors, selected from the group consisting of thiazole vulcanization accelerators, mercapto vulcanization accelerators, sulfenamide vulcanization accelerators, thiocarbamate vulcanization accelerators, thiuram vulcanization accelerators, thiophosphate vulcanization accelerators, thiourea vulcanization accelerators, xanthogenate vulcanization accelerators and guanidine vulcanization accelerators.

[0144] N-cyclohexyl-2-benzothiazole sulfenamide (CBS), It is preferred to use a sulfenamide accelerator selected from N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazyl-2-sulfene morpholide (MBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and guanidine accelerators such as diphenylguanidine (DPG).

[0145] The sulfur donor material used can be selected from any of the sulfur donor materials known to those of skill in the art.

[0146] Vulcanization retarders may also be present in the rubber mixture.

[0147] The preparation of the rubber mixtures of the present invention is preferably carried out by the processes conventional in the rubber industry, in which a primary mixture containing all the components except the vulcanization system (e.g. sulfur and vulcanization-affecting substances) is first prepared in one or more mixing stages, and the final mixture is produced by adding the vulcanization system in the final mixing stage.

[0148] The final mixture may be further processed, for example, and brought into a suitable shape by an extrusion operation or by calendering.

[0149] The rubber mixture of the present invention is particularly suitable for use in vehicle tires, especially pneumatic vehicle tires.In principle, it is possible to use it in all tire components, especially in the outer components, especially preferably in the flange profile, the tread and / or the sidewall.In the case of a tread having a cap / base structure, it is preferred that the rubber mixture of the present invention is used at least in the cap.

[0150] For use in vehicle tires, the mixture as a finished pre-vulcanized mix is ​​preferably formed into the corresponding shape of the outer component and applied in known manner during the manufacture of green vehicle tires.

[0151] The manufacture of the rubber mixture of the invention for use as any other body mix in vehicle tires is carried out as described above. The difference lies in the shaping after the extrusion operation / calendering of the mixture. The shape of the rubber mixture thus obtained, not yet vulcanized, for one or more different body mixes is then subjected to the manufacture of green tires.

[0152] Here, "body mix" refers essentially to the rubber mix for the inner components of the tire, such as the squeegee, inner liner (inner layer), core profile, belt, shoulder, belt profile, carcass, bead reinforcement, bead profile, flange profile and bandage.

[0153] The green tire, which is not yet cured, is then cured.

[0154] For the use of the rubber mixture of the invention in drive belts and other belts, in particular conveyor belts, the extruded, not yet vulcanized mixture is brought into a suitable shape and is often provided, simultaneously or subsequently, with reinforcing elements, such as synthetic fibers or steel cords, usually resulting in a multi-ply structure consisting of one and / or several plies of the rubber mixture, one and / or several plies of identical and / or different reinforcing elements and one and / or several further plies of the same and / or other rubber mixtures.

[0155] The present invention further provides a vehicle tyre comprising a rubber mixture according to the invention containing in at least one of its constituents a compound according to the invention.

[0156] The vulcanized vehicle tire in at least one component contains a vulcanizate of at least one rubber mixture according to the invention. It is known to those skilled in the art that most substances present, such as rubber, may be present already after mixing or only after vulcanization in a chemically modified form.

[0157] In the context of this invention, "vehicle tires" means pneumatic vehicle tires and solid rubber tires, including industrial tires, as well as tires for construction vehicles, trucks, cars and motorcycles.

[0158] It is preferred if the vehicle tyre according to the invention comprises the rubber mixture according to the invention in at least one external component, which external component is preferably the tread, the sidewall and / or the flange profile.

[0159] The vehicle tyre according to the invention may therefore comprise a rubber mixture according to the invention comprising an inventive compound of formula I) in two or more components, optionally with a compatible composition. EXAMPLES

[0160] The present invention will now be more particularly described with reference to exemplary embodiments.

[0161] Compounds of formula III) as exemplary embodiments of compounds of formula I) are prepared in the manner shown in Schemes S1a) and S2) below: [ka] In the formula, AcOH represents acetic acid, and the synthesis was carried out according to Scheme S1a) by BADalvi, Tet. Lett., 2018, 59, 2145-2149.

[0162] Synthesis of 6-(1,3-dimethylbutylamino)-2,3,4,9-tetrahydro-1H-carbazole (compound of formula III): [ka] 0.30 g (1.39 mmol, 1 equivalent (equivalent)) of 6-nitro-2,3,4,9-tetrahydro-1H-carbazole, 0.12 g (0.4 g on 4.67 mmol substrate) of platinum on activated carbon (5%) and 20.0 ml of methyl isobutyl ketone were weighed into a stainless steel autoclave fitted with a Teflon inliner. The reaction mixture was then subjected to hydrogen at a pressure of 20 bar and stirred at 60° C. for 10 hours. After the reaction was complete, the excess hydrogen was released and the suspension was filtered through Celite® and washed with ethanol. The filtrate was concentrated to dryness and dried under reduced pressure. Greyish solid; yield 0.37 g (98% of theory). 1 H-NMR (Nuclear Magnetic Resonance) (500MHz,DMSO-d6)δ=10.07(s,1H),6.95(d,J=8.5Hz,1H),6.45(d,J =2.1Hz,1H),6.39(dd,J=8.5,2.1Hz,1H),4.36(s,1H),3.41(q,J=6.4Hz,1H),2.63 (t,J=5.9Hz,2H),1.84-1.69(m,7H),1.46(dt,J=13.8,7.0Hz,1H),1.18(dt,J=13. 5,6.8Hz,1H),1.07(d,J=6.1Hz,3H),0.92(d,J=6.6Hz,3H),0.90(d,J=6.6Hz,3H). 13 C-NMR(126MHz,DMSO-d6)δ=141.7,134.5,129.5,128.6,111.3,110.5,107 .4,99.8,47.2,46.7,26.8,25.1,23.6,23.5,23.4,23.4,23.0,21.3,21.3. ESI-MS (electrospray ionization mass spectrometry) [M+H] + =271.

[0163] Measurement of oxidative induction time (OIT) The compound of formula III) was studied under laboratory conditions with regard to its potential protective effect as an ageing stabilizer by measuring the oxidation induction time.

[0164] For this purpose, the compound of formula III and 6PPD were mixed with a polymer (liquid synthetic polyisoprene (IR), LIR-50, Kuraray, weight average molecular weight distribution M w = 54000g / mol, glass transition temperature T g =-63°C) and heated at a constant temperature (180°C) until the onset of oxidation (starting temperature 35°C, heating rate of 20 K / min (Kelvin / min) to 170°C, heating rate of 1 K / min to 180°C; purge gas: nitrogen (N2), volume flow rate 50 ml / min).

[0165] The test piece was kept under isothermal conditions of 180° C. in an N2 atmosphere for 5 minutes, and then the atmosphere was switched to an O2 atmosphere (volume flow rate 50 ml / min).

[0166] DSC (differential scanning calorimetry) was used to determine the oxidation via peaks.

[0167] The time (min) until oxidation was measured.

[0168] The results compared with the known aging stabilizer 6PPD are summarized in Table 1.

[0169] [Table 1]

[0170] Considering the measurement accuracy of ±(plus / minus) 10 minutes, it is clear that the compound of formula III) achieves an antioxidant effect comparable to that of 6PPD at 180°C.

[0171] The inventive compounds of the formula III), as representatives of the inventive compounds of the formula I), are therefore more environmentally friendly and less harmful to health than 6PPD / further representatives of the substance classes as mentioned above, and are also comparable ageing stabilizers.

[0172] At the same time, the inventive compounds of the formula III), as representatives of the inventive compounds of the formula I), show very good solubility in rubber mixtures, which prevents blooming and thus improves the protective effect.

[0173] The compounds of formula I) therefore make it possible to achieve, for the possible applications described, a comparable or even improved protective effect in terms of reduced blooming behavior.

[0174] For use in rubber mixtures for vehicle tyres, the compounds of the invention of formula I), e.g. of formula III), are added in one of the mixing stages during the preparation of the rubber mixture in a manner known to those skilled in the art, instead of ageing stabilizers known to those skilled in the art, such as, for example, 6PPD, 7PPD or IPPD.

[0175] For this purpose, the compound of formula III) is incorporated in various amounts, as an example, as shown in Table 2. The obtained examples of the invention are identified as E1 and E2.

[0176] For comparison, rubber mixtures containing 6PPD instead of the compound of formula III) are used as aging stabilizers with otherwise identical compositions, in each case substituting on a mole per mole basis between V1 and E1 and between V2 and E2. The amounts in Table 2 are reported in phr. A reference (Ref.) without aging stabilizer is also reported.

[0177] In all mixtures, the sum of the amounts of aging stabilizer (6PPD or formula III) and plasticizer oil MES is 10 phr.

[0178] [Table 2]

[0179] The examples of the present invention show comparable or even improved aging stabilization effects compared to rubber mixtures containing 6PPD.

Claims

1. Formula I): 【Chemistry 1】 wherein R １ xi) an aromatic group optionally having a substituent selected from the group consisting of a halogen group, a cyano group, an ester group, a ketone group, an ether group and a thioether group; and xii) linear, branched and cyclic aliphatic C ３ ~C １２ is selected from the group consisting of group R ２ and R ３ may be the same or different, independently of one another, and are linear, branched and cyclic, saturated and unsaturated, aliphatic C １ ~C １２ groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups, with fluorine, bromine and chlorine being preferred, cyano groups, ester groups, ketone groups, ether groups and thioether groups; m takes the value 0, 1, 2, or 3; The compound wherein n has a value of 0 or is an integer from 1 to 8, preferably from 1 to 4.

2. Formula II): 【Chemistry 2】 wherein R １ , R ２ , R ３ 2. The compound according to claim 1, characterized in that m and n are as defined in claim 1.

3. 3. A compound according to claim 1 or 2, characterized in that m is zero (0) and / or n is zero (0).

4. R １ The compound according to any one of claims 1 to 3, characterized in that: is bonded to the nitrogen atom (N) via a tertiary carbon atom.

5. R １ Compounds according to any one of claims 1 to 4, characterized in that is a branched and / or cyclic alkyl radical having 3 to 12 carbon atoms, preferably having 3 to 8 carbon atoms.

6. R １ is selected from 1,3-dimethylbutyl radicals and cyclohexyl radicals; R １ Compounds according to any one of claims 1 to 5, characterized in that is preferably a 1,3-dimethylbutyl radical.

7. Formula III): 【Chemistry 3】 The compound according to any one of claims 1 to 6, characterized in that it has the structure:

8. A rubber mixture comprising a compound according to any one of claims 1 to 7, preferably comprising at least one diene rubber selected particularly preferably 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.

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

10. 8. Use of the compounds according to any one of claims 1 to 7 as ageing stabilizers and / or antiozonants, in particular in vehicle tyres and / or other industrial rubber articles, such as, in particular, air springs, bellows, conveyor belts, straps, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical or robotic applications or shoe soles or parts thereof, and / or in oils and / or lubricants.

11. Use of a compound according to any one of claims 1 to 7 for the manufacture of rubber articles, in particular air springs, bellows, conveyor belts, straps, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical or robotic applications, or shoe soles or parts thereof.

12. A process for preparing a compound of formula I comprising the following process steps: i) producing or providing a substance of formula B1): 【Chemistry 4】 ii) reacting the compound of formula B1) with hydrogen and a ketone or aldehyde, preferably a ketone, to obtain the compound of formula I): 【Chemistry 5】 wherein R １ xi) an aromatic group optionally having a substituent selected from the group consisting of a halogen group, a cyano group, an ester group, a ketone group, an ether group and a thioether group; and xii) linear, branched and cyclic aliphatic C ３ ~C １２ is selected from the group consisting of group R ２ and R ３ may be the same or different, independently of one another, and are linear, branched and cyclic, saturated and unsaturated, aliphatic C １ ~C １２ groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups, with fluorine, bromine and chlorine being preferred, cyano groups, ester groups, ketone groups, ether groups and thioether groups; m takes the value 0, 1, 2, or 3; The process wherein n takes the value 0 or is an integer from 1 to 8, preferably from 1 to 4.

13. 13. The process according to claim 12, wherein the reaction of step ii) is carried out using a hydrogenation catalyst and / or hydrogen at a temperature of from 50° C. to 130° C., preferably from 50° C. to 100° C., particularly preferably from 50° C. to 80° C., and / or the reaction mixture is subjected to hydrogen at a pressure of, for example, from 10 to 70 bar, particularly preferably from 10 to 30 bar, in particular 20 bar, and the reaction is carried out in an autoclave or another pressure reactor.

14. The compound of formula I) is represented by formula II: 【Chemistry 6】 The structure is The substance of formula B1) is a compound of formula B1a): 【Chemistry 7】 wherein R １ , R ２ , R ３ 14. The process according to claim 12 or 13, characterized in that m and n are as defined in claim 12.

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