EP4373677A1

EP4373677A1 - Compound, rubber blend containing the compound, vehicle tire comprising the rubber blend in at least one component, process for producing the compound, and use of the compound as an ageing protectant and/or antiozonant and/or dye

Info

Publication number: EP4373677A1
Application number: EP22738540.8A
Authority: EP
Inventors: Andreas Jacob; David-Raphael DAUER; Julian STROHMEIER
Original assignee: Continental Reifen Deutschland GmbH
Current assignee: Continental Reifen Deutschland GmbH
Priority date: 2021-07-23
Filing date: 2022-06-14
Publication date: 2024-05-29
Also published as: DE102021207928A1; WO2023001341A1; CN117693430A; KR20240058842A

Abstract

The invention relates to a compound, a rubber blend containing said compound, a vehicle tire comprising the rubber blend in at least one component, a process for producing the compound and the use of the compound as ageing protectant and/or antiozonant and/or dye. The compound according to the invention has the formula (I) wherein R¹ is selected from the group consisting of xi) aromatic groups, the aromatic groups optionally carrying substituents that are selected from the group consisting of halogen groups, cyano groups, ester groups, ketone groups, ether groups and thioether groups, and xii) linear, branched and cyclic aliphatic C₄ to C₁₂ groups, and xiii) combinations of aromatic with aliphatic C₁ to C₁₂ groups.

Description

description

compound, rubber compound containing the compound,

Vehicle tire which has the rubber mixture in at least one component, method for producing the compound and use of the compound as anti-aging agent and/or anti-ozone agent and/or dye

The invention relates to a compound, a rubber compound containing the compound, a vehicle tire which has the rubber compound in at least one component, a method for producing the compound and the use of the compound as an aging inhibitor and/or antiozonant and/or dye.

It is known that polymeric materials, such as rubbers in particular, are used in vehicle tires and technical rubber articles.

Natural rubber, synthetic polymers (such as IR, BR, SSBR, ESBR, etc.) but also natural and synthetic oils, greases and lubricants are subject to oxidation reactions when stored for a long period of time and especially in the target application, which often takes place at higher temperatures, which can have adverse effects affect the original desired properties. Depending on the type of polymer, the polymer chains are shortened to the point of liquefying the material, or the material is subsequently hardened.

Anti-aging agents therefore make a significant contribution to the longevity of vehicle tires and other technical rubber items.

Known antioxidants are aromatic amines, such as 6-PPD (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 molecules can react with oxygen or ozone or radicals formed, such as alkyl, alkoxy and alkylperoxy radicals, and thus intercept them and thus protect the rubber, etc. from further oxidation reactions.

The disadvantage of this class of substances, however, is the suspicion that they could be carcinogenic.

Anti-aging agents that react with ozone in particular and intercept it are also referred to as “ozone protection agents” or “antiozonants”.

The invention is based on the object of providing a novel compound which can be used in particular as an anti-aging agent in vehicle tires or other technical rubber articles with a lower risk potential and sufficient solubility in the respective matrix, for example and in particular in the polymer. This is intended to ensure continued optimal protection against oxygen and ozone while reducing the health hazards and to prevent the tendency to bloom.

The object is achieved by the compound according to the invention as claimed in claim 1, the rubber mixture according to the invention containing the compound and the vehicle tire according to the invention which has the rubber mixture according to the invention in at least one component.

Furthermore, the object is achieved through the use of the compound as an anti-aging agent and/or an anti-ozone agent.

The compound according to claim 1 can further be used as a dye. Furthermore, the object is achieved by methods according to the invention for preparing the compound according to the invention.

The compound according to claim 1 has the general formula I): wherein R ¹ is selected from the group consisting of xi) aromatic residues, the aromatic residues optionally having substituents selected from the group consisting of halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether radicals, and xii) linear, branched and cyclic aliphatic C4 to C12 radicals, and xiii) combinations of aromatic and aliphatic C1 to C12 radicals; and wherein the radicals R ² and R ³ independently can be the same or different and are selected from the group consisting of linear, branched and cyclic, saturated and unsaturated, aliphatic C to C-12 radicals which optionally contain one or more halogen -Carry substituents, aryl radicals, which optionally carry one or more halogen substituents, and halogen radicals, fluorine, bromine and chlorine being preferred, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether radicals radicals, and where n is 0 or 1 or 2 or 3 or 4, where the radicals R ³ are independently identical or different when n is 2 or 3 or 4, and where m is 0 or 1 or 2 or 3, where the R ² radicals are independently the same or different when m is 2 or 3.

It is preferred that R ¹ is selected from the group consisting of benzyl and linear, branched and cyclic aliphatic C4 to C12 radicals; and where R ³ is selected from the group consisting of linear, branched and cyclic aliphatic Ci - to Ci2 radicals, and aryl radicals, cyano radicals, halogen radicals, with fluorine, bromine and chlorine being preferred, ether radicals and thioether radicals, and where n is 0 or 1 or 2 or 3 or 4, where the radicals R ³ are independently the same or different when n is 2 or 3 or 4, and where R ² is selected from the group consisting of linear, branched and cyclic aliphatic Ci - to Ci2 radicals, and aryl radicals, cyano radicals, halogen radicals, with fluorine, bromine and chlorine being preferred, ether radicals and thioether -leftovers; and where m has the value 0 or 1 or 2 or 3, where the radicals R ² are independently identical or different when m is 2 or 3.

It is clear to the person skilled in the art that when n is 0 (zero) or 1 or 2 or 3, instead of R ³ , a hydrogen atom is bonded to the corresponding carbon atom of the benzene ring. Likewise, when m is 0 or 1 or 2, all other vacant positions on the benzene ring of the backbone are hydrogen atoms.

Those skilled in the art will also appreciate that the representation of the linkages of (R ² ) _m and (R ³ ) _n and R ¹ HN in the respective benzene ring of the skeleton means that each of these groups can be located anywhere on the respective benzene ring, except of course not two or more in the same position at the same time, which would be impossible due to the tetrabond nature of the carbon atom of the benzene ring.

In the context of the present invention, designations such as “C4 to C12 radicals” mean that radicals having 4 to 12 carbon atoms are meant. Irrespective of this, "Ci" is used to designate the position of the most oxidized carbon atom or the highest priority after the

Cahn-Ingold-Prelog Convention (CIP) used. It is clear to the person skilled in the art in the respective context what is meant.

The compound according to the invention is an acridinone derivative and has a lower risk potential than known anti-aging agents based on aniline (possible cleavage product of 6-PPD). If one compares the safety data sheets for the base substances aniline and acridinone, it is striking that, in contrast to aniline, acridinone is neither mutagenic nor mutagenic. This is a decisive advantage, especially in a technical application such as in vehicle tires or other rubber products, since the rubber ingredients can be released through abrasion or other degradation processes. Compared to 6-PPD, the compound according to the invention also has an improved protective effect, in particular of polymers, against oxidation and thus aging.

All advantageous configurations, which are reflected in the patent claims, among other things, are included in the invention. In particular, the invention also includes configurations that result from the combination of different features of different gradations when these features are preferred, so that a combination of a first feature referred to as “preferred” or a feature described in the context of an advantageous embodiment with a further feature, e.g. B. "particularly preferred" designated feature is covered by the invention.

The radicals R ² and R ³ are independently identical or different and are selected from the group consisting of linear, branched and cyclic, saturated and unsaturated, aliphatic Ci - to Ci2 radicals, which optionally carry one or more halogen substituents, aryl radicals which optionally carry one or more halogen substituents, and halogen radicals, with fluorine, bromine and chlorine being preferred, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether radicals.

The radicals R ² and R ³ mentioned can already be attached to the respective benzene ring or its precursor, in particular through the selection of suitable starting substances.

Preferably n is 0 (zero).

Preferably m is 0 (zero).

The radical R ¹ is selected from the group consisting of xi) aromatic radicals, where the aromatic radicals optionally have substituents selected from the group consisting of halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether residues, and xii) C3 to C12 linear, branched and cyclic aliphatic radicals, especially C4 to C12 radicals, and xiii) combinations of C1 to C12 aromatic and aliphatic radicals.

The aromatic radical from subgroup xi) is, for example and preferably, a phenyl radical.

The aromatic radicals of subgroup xi) can carry substituents. As stated above, these are selected from the group consisting of halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether radicals.

The substituents are preferably selected from the group consisting of ester residues, ketone residues, ether residues and thioether residues.

According to preferred embodiments, the aromatic radical is not substituted on the two C atoms which are adjacent to the Ci atom, ie the carbon atom which is bonded to the N atom. In the case of a benzene ring as the basic skeleton, there is preferably no substituent in the ortho-position to the N atom.

According to further preferred embodiments, the aromatic radical of subgroup xi) is unsubstituted.

It is preferred that R ¹ is bonded to the nitrogen atom (N) through a tertiary carbon atom. The Ci atom is therefore preferably a tertiary carbon atom. In the context of the present invention, the term “tertiary carbon atom” means a carbon atom which is bonded to only one hydrogen atom.

This results in - against secondary and quaternary carbon atoms - a particularly good protective effect due to the presence of the compound in rubber mixtures, in particular for vehicle tires and other technical rubber articles, and in particular an optimized reactivity in connection with the mechanisms relevant to aging protection, with undesirable side reactions being avoided will. The mixed aromatic and aliphatic radical from subgroup xiii) is, for example and preferably, selected from the group consisting of benzyl and 1-phenylalkyl radicals having a total of 7 to 18 carbon atoms, in particular selected from benzyl and 1-phenylethyl radicals, where 1 -Phenylalkyl radicals, in particular 1-phenylethyl, are particularly preferred because of the tertiary carbon atom.

According to further advantageous embodiments, R ¹ is a branched or cyclic alkyl radical having three to twelve carbon atoms, preferably three to eight carbon atoms, where R ¹ is particularly preferably selected from

1.3-dimethylbutyl and cyclohexyl radicals, where R ¹ is very particularly preferably one

1.3-dimethylbutyl radical.

This achieves particularly good solubility in rubber mixtures for vehicle tires and other technical rubber items.

In a preferred embodiment, the compound has the structure according to formula II):

With the compound of the formula II), in particular in polymers, it is even possible to achieve a further improvement in the protection against oxidation and thus aging. At the same time, the compound of formula II) is significantly less harmful than z. B. 6-PPD or other representatives of this class of substances, as listed in the introduction.

In comparison to 6-PPD, the compound according to formula II) is therefore a better and at the same time more health-friendly and environmentally friendly anti-aging agent. The compound according to the invention according to formula I) or formula II) or all of the above statements is particularly useful as an anti-aging agent and/or anti-ozone agent in vehicle tires and/or technical rubber articles, such as in particular an air spring, a bellows, conveyor belt, belt, belt, hose, rubber band , profile, a seal, a membrane, tactile sensors for medical applications or robotic applications, or a shoe sole or parts thereof, and/or oils and/or lubricants.

A further object of the present invention is therefore the use of the compound according to the invention as an anti-aging agent and/or an anti-ozone agent in vehicle tires and/or technical rubber articles, such as in particular an air spring, a bellows, a conveyor belt, a belt, a belt, a hose, a rubber band, a profile, a seal, a membrane, tactile sensors for medical applications or robotic applications, or a shoe sole or parts thereof, and/or oils and/or lubricants.

To use the compound according to formula I) or formula II) or all of the above statements in the articles or substances mentioned, it is used in a composition and mixed into it.

In the case of vehicle tires or other technical rubber items, this is in particular a rubber mixture.

Another object of the invention is the use of the compound according to the invention of formula I) or formula II) or all of the above statements as a dye in fibers and/or polymers and/or paper and/or in paints and varnishes.

A further aspect of the present invention is a process for preparing the compound of the formula I), which comprises the following process steps: a) providing the compounds of the formula A) and B) b) Reaction of the compounds A) and B) with one another in the presence of a base and a catalyst, the compound of the formula C) being obtained: c) Reaction of the compound of the formula C) with hydrogen or a flydriating reagent, in particular a hydride, and a ketone or aldehyde (R ¹ =0), to form the compound of the formula D): d) optional conversion of the compound according to formula D) to the compound according to formula E): e) Reaction of the compound of the formula D) or E) with an acid to give the compound of the formula I): All of the above statements apply to the radicals R ¹ , R ² and R ³ and the indices m and n.

The base in step b) is preferably selected from organic and inorganic bases. The inorganic base is preferably selected from the group consisting of potassium carbonate, potassium phosphate, sodium carbonate, sodium phosphate, cesium carbonate.

The organic base is preferably selected from the group consisting of sodium Fe/f-butoxide, potassium Fe/f-butoxide.

The catalyst in step b) is preferably a catalyst which catalyzes via a “copper coupling”, such as in particular copper iodide.

In the case of copper coupling, an inorganic base is preferably used, e.g. B. copper iodide as a catalyst in combination with the base potassium carbonate. A “palladium coupling” is also preferred, where the catalyst optionally has mono- or polydentate ligands, in particular mono- or polydentate phosphine ligands. Suitable catalysts are in particular and for example triphenylphosphine and binaphthylphosphine (BINAP).

Both an inorganic and an organic base can be used in copper coupling.

By "hydrogenation reagent" is meant a compound that enables hydrogenation. These include, as is known to those skilled in the art, hydrides, in particular metal hydrides.

A suitable hydride is e.g. B. sodium borohydride.

In the context of the present invention, hydrogen is not additionally listed under “hydrogenation reagent” since it is explicitly mentioned as an alternative. Naturally however, all reagents that generate hydrogen in situ that cause hydrogenation are included under “hydrogenation reagent”.

The reaction in step c) is preferably carried out with hydrogen (H2) and the ketone or aldehyde, preferably ketone, using a hydrogenation catalyst and preferably at a temperature of 50 to 70° C., in particular 60° C., for example.

Hydrogen is preferably injected at a pressure of 15 to 25 bar, in particular 20 bar, for example, and stirring is then preferably carried out for 1 to 20 hours, preferably 8 to 13 hours, in particular 10 hours, for example.

The ketone in step c) is the ketone derivative of the later radical R ¹ ; With an aldehyde corresponding to the aldehyde derivative.

For the sake of simplicity, the formula R ¹ =0 for the aldehyde or ketone is used in abbreviated form, since the radical R ¹ is the part which remains on the nitrogen atom after the reaction with the aldehyde or ketone.

The ketone methyl isobutyl ketone is preferably used here.

The reaction with hydrogen in step c) preferably takes place in a container suitable for the comparatively high pressures, such as in particular an autoclave or another pressure reactor.

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

A ketone or aldehyde, particularly preferably ketone, in liquid form is preferably used as the solvent. As a result, an additional substance such as toluene or xylene can be dispensed with. A suitable catalyst, referred to as “hydrogenation catalyst” in the context of the present invention, is preferably used in the process steps in which a reaction with hydrogen takes place.

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

Other known catalysts such as Raney nickel or copper chromite can also be used.

Reaction with a base is optional. The compound of the formula D) can also be reacted directly with an acid to give the target compound of the formula I). Here, sulfuric acid (H2SO4) is used in particular and for example as the acid.

However, the reaction according to step d) preferably takes place first.

This achieves a higher yield of the target compound of the formula I). The conversion of the compound according to formula D) into the compound according to formula E) represents an ester cleavage and is preferably carried out with a reagent suitable for this purpose, in particular with a base, for example sodium hydroxide (NaOH), or an acid, for example concentrated hydrochloric acid (conc. HCl).

The reaction in step d) is preferably heated under reflux for several hours. Preference is given to heating for 4 to 12 hours, particularly preferably 6 to 10 hours, for example 8 hours (overnight), and then cooling.

The pH is then preferably adjusted to 6.8 to 7.2, in particular 7, preferably with ice cooling.

This is followed by extraction with a solvent. 2-Methyltetrahydrofuran (2-MTHF) is preferably used here and the extraction is carried out several times, in particular three times. By the use of 2-Methyltetrahydrofuran (2-MTHF) a particularly high yield of the intermediate compound according to formula E) is achieved.

If step d) has been carried out beforehand, the compound of the formula E) is reacted with an acid. Polyphosphoric acid (PPA) is used here, for example and preferably.

The reaction in step e) is preferably carried out at a temperature of from 120 to 140.degree. C., for example 130.degree. It is then preferably first cooled to a temperature of 50 to 70° C. and unreacted acid is hydrolyzed with water. Subsequently, it is preferably further cooled to room temperature (RT). The pH is then preferably adjusted to 6.8 to 7.2, in particular 7. This results in particularly high yields of the target compound of the formula I).

This is followed by extraction with a solvent. 2-Methyltetrahydrofuran (2-MTHF) is preferably used here and the extraction is carried out several times, in particular twice. A particularly high yield of the target compound is also achieved by using 2-methyltetrahydrofuran (2-MTHF).

A further subject of the present invention is a further process for preparing the compound of the formula I), which comprises at least the following process steps: a1) providing the compound of the formula A1)

A1) where the above statements apply to the radicals R ² , R ³ and the indices m and n and X is a halogen, in particular fluorine (F), chlorine (Cl) or bromine (Br); b1) Reaction of the compound of the formula A1) with a base, in particular potassium carbonate (K2CO3), the compound of the formula B1) being obtained: B1) c1) Reaction of the compound of the formula B1) with hydrogen or a hydrogenating reagent, in particular a hydride, and a ketone or aldehyde (R ¹ =0), to form the compound of the formula I):

The base in step b1) is preferably a strong base such as potassium carbonate (K2CO3) or potassium phosphate (K3PO4). Potassium carbonate (K2CO3) is particularly preferably used.

The reaction according to step b1) preferably takes place in a polar solvent, such as in particular dimethylformaldehyde (DMF) or dimethyl sulfoxide (DMSO). Dimethylformaldehyde (DMF) is particularly preferably used. The reaction in step c1) preferably takes place with hydrogen and the ketone or aldehyde, preferably ketone, using a hydrogenation catalyst and preferably at a temperature of 120 to 150° C., in particular 140° C., for example. Hydrogen is preferably injected at a pressure of 35 to 45 bar, in particular 40 bar, for example, and stirring is then preferably carried out for 1 to 20 hours, preferably 8 to 13 hours, in particular 10 hours, for example.

The ketone methyl isobutyl ketone is preferably used here.

A suitable catalyst, referred to as “hydrogenation catalyst” in the context of the present invention, is preferably used in the process steps in which a reaction with hydrogen takes place.

Furthermore, other known catalysts such as Raney nickel or copper chromite can be used.

The solvent in step c1) can be either the ketone or aldehyde when in liquid form, or an inert solvent such as toluene or xylene, especially when the ketone or aldehyde is in solid form. In the latter case, the ketone or aldehyde is used only in stoichiometric amounts as the reactant.

A ketone or aldehyde, particularly preferably ketone, in liquid form is preferably used as the solvent. As a result, an additional substance such as toluene or xylene can be dispensed with.

The reaction product of the above-described method according to the invention is in particular a mixture of substances comprising the compound of the formula I), with purification preferably taking place after step c1) or e), for example by column chromatography, for example on silica gel. A further object of the invention, as stated above, is a rubber mixture.

The rubber mixture according to the invention contains the compound of the formula I), in particular of the formula II). In principle, the rubber mixture according to the invention can be any rubber mixture, in particular in which the novel compound according to the invention of formula I), in particular of formula II), acts as an anti-aging agent and/or antiozonant with lower toxicity.

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

The rubber mixture according to the invention preferably contains 0.1 to 10 phr, particularly preferably 0.1 to 7 phr, very particularly preferably 1 to 6 phr, of the compound of the formula I), in particular of the formula II).

The specification phr (parts per hundred parts of rubber by weight) used in this document is the quantity specification for compound formulations customary in the rubber industry. In this document, the dosage of the parts by weight of the individual substances is based on 100 parts by weight of the total mass of all high molecular weight (Mw greater than 20,000 g/mol) rubbers present in the mixture.

According to advantageous embodiments of the invention, the rubber mixture according to the invention contains at least one diene rubber.

The rubber mixture can thus contain a diene rubber or a mixture of two or more different diene rubbers.

Diene rubbers are rubbers which are formed by polymerization or copolymerization of dienes and/or cycloalkenes and thus have C=C double bonds either in the main chain or in the side groups. The diene rubber is preferably selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), epoxidized polyisoprene (ENR), butadiene rubber (BR), butadiene-isoprene rubber, solution-polymerized styrene-butadiene rubber (SSBR ), emulsion-polymerized styrene-butadiene rubber (ESBR), styrene-isoprene rubber, liquid rubbers with a molecular weight Mw greater than 20000 g/mol, halobutyl rubber, polynorbornene, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber ,

nitrile rubber, chloroprene rubber, acrylate rubber, fluorine rubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-butadiene terpolymer, hydrogenated acrylonitrile-butadiene rubber and hydrogenated styrene-butadiene rubber.

In particular, nitrile rubber, hydrogenated acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, flalobutyl rubber and/or ethylene propylene diene rubber are used in the manufacture of technical rubber articles such as belts, belts and hoses and/or shoe soles. The mixture compositions known to those skilled in the art for these rubbers, which are particular with regard to fillers, plasticizers, vulcanization systems and additives, are preferably used.

The natural and/or synthetic polyisoprene of all embodiments can be either cis-1,4-polyisoprene or 3,4-polyisoprene. However, preference is given to using cis-1,4-polyisoprenes with a cis-1,4 content>90% by weight. On the one hand, such a polyisoprene can be obtained by stereospecific polymerization in solution with Ziegler-Natta catalysts or using finely divided lithium alkyls. On the other hand, natural rubber (NR) is a cis-1,4-polyisoprene in which the cis-1,4 content in the natural rubber is greater than 99% by weight.

A mixture of one or more natural polyisoprenes with one or more synthetic polyisoprene(s) is also conceivable. As used herein, the term "natural rubber" means naturally occurring rubber that can be obtained from Hevea rubber trees and "non-Hevea" sources. Non-Hevea sources include guayule shrubs and dandelions such as TKS (Taraxacum kok-saghyz; Russian dandelion).

If butadiene rubber (=BR, polybutadiene) is contained in the rubber mixture according to the invention, it can be of any type known to the person skilled in the art. These include the so-called high-cis and low-cis types, polybutadiene with a cis content greater than or equal to 90% by weight being the high-cis type and polybutadiene with a cis content of less than 90% by weight. % is called the low-cis type. An example of a low cis polybutadiene is Li-BR (lithium catalyzed butadiene rubber) having a cis content of 20 to 50% by weight. Particularly good properties and low hysteresis of the rubber compound are achieved with a high-cis BR.

The polybutadiene(s) used can/can be end-group-modified with modifications and functionalizations and/or functionalized along the polymer chains. The modification can involve those with hydroxyl groups and/or ethoxy groups and/or epoxy groups and/or siloxane groups and/or amino groups and/or aminosiloxane and/or carboxy groups and/or Act phthalocyanine groups and / or silane sulfide groups. However, other modifications known to those skilled in the art, also referred to as functionalizations, are also possible. Metal atoms can be part of such functionalizations.

If at least one styrene-butadiene rubber (styrene-butadiene copolymer) is contained in the rubber mixture, it can be either solution-polymerized styrene-butadiene rubber (SSBR) or emulsion-polymerized styrene-butadiene rubber (ESBR ) act, in which case a mixture of at least one SSBR and at least one ESBR can also be used. The terms “styrene-butadiene rubber” and “styrene-butadiene copolymer” are used synonymously in the context of the present invention. The styrene-butadiene copolymer used can be end-group-modified with the modifications and functionalizations mentioned above for polybutadiene and/or functionalized along the polymer chains.

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.

According to a particularly preferred embodiment of the 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).

According to a particularly advantageous embodiment of the invention, the rubber mixture contains at least one natural polyisoprene (NR) and/or synthetic polyisoprene (IR), preferably in amounts of 50 to 100 phr, and according to a particularly advantageous embodiment of the invention 80 to 100 phr, entirely more preferably 95 to 100 phr, again preferably 100 phr. A rubber mixture of this type shows in particular optimized tear properties and abrasion properties with good processability and reversion stability.

If the rubber mixture contains less than 100 phr NR and/or IR, it preferably contains at least one diene rubber selected from the group consisting of butadiene rubber (BR), solution-polymerized styrene-butadiene rubber ( SSBR) and emulsion polymerized styrene butadiene rubber (ESBR).

According to a further particularly advantageous embodiment of the invention, the rubber mixture contains at least one natural polyisoprene (NR), preferably in amounts of 5 to 55 phr, and according to a particularly advantageous embodiment of the invention 5 to 25 phr, most preferably 5 to 20 phr. A rubber mixture of this type shows, in particular, good processability and reversion stability, as well as optimized tear properties and optimum rolling resistance behavior.

According to a further particularly advantageous embodiment of the invention, the rubber mixture contains at least one polybutadiene (BR, butadiene rubber), preferably in amounts of 10 to 80 phr, particularly preferably 10 to 50 phr, and according to a particularly advantageous embodiment of the invention 15 to 40 phr. This achieves particularly good tear and abrasion properties for the rubber mixture according to the invention and optimum braking performance.

According to a further particularly advantageous embodiment of the invention, the rubber mixture contains at least one solution-polymerized styrene-butadiene rubber (SSBR), preferably in amounts of 10 to 80 phr, particularly preferably 30 to 80 phr, and according to a particularly advantageous embodiment of the invention 50 to 70 phr. This achieves particularly good rolling resistance properties for the rubber mixture according to the invention. According to particularly advantageous embodiments of the invention, SSBR is used in combination with at least one other rubber in order to achieve an optimal and balanced property profile.

The rubber mixture preferably contains at least one filler, preferably in amounts of 30 to 500 phr, particularly preferably 50 to 400 phr, again preferably 80 to 300 phr.

According to advantageous embodiments of the invention, the filler is a reinforcing filler, preferably selected from the group consisting of carbon blacks and silica.

Suitable carbon blacks are all types of carbon black known to those skilled in the art. The carbon black is preferably selected from carbon blacks and pyrolysis carbon blacks, carbon blacks being more preferred. The carbon black preferably has an iodine number, according to ASTM D 1510, which is also referred to as the iodine adsorption number, between 30 and 250 g/kg, preferably 30 to 180 g/kg, particularly preferably 40 to 180 g/kg, and very particularly preferably 40 to 130 g/kg, and a DBP number according to ASTM D 2414 of 30 to 200 ml/100 g, preferably 70 to 200 ml/100 g, particularly preferably 90 to 200 ml/100 g.

The DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light-colored filler using dibutyl phthalate.

The use of such a type of carbon black in the rubber compound, especially for vehicle tires, ensures the best possible compromise between abrasion resistance and heat build-up, which in turn influences the ecologically relevant rolling resistance.

Particularly suitable and preferred is a carbon black with an iodine adsorption number of between 80 and 110 g/kg and a DBP number of 100 to 130 ml/100 g, such as in particular carbon black of the N339 type.

The silica is preferably amorphous silica, for example precipitated silicic acid, also referred to as precipitated silica. Alternatively, for example, pyrogenic silicon dioxide can also be used.

However, it is particularly preferred if a finely divided, precipitated silica is used which has a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) from 35 to 400 m ² /g, preferably from 35 to 350 m ² / g, more preferably from 85 to 320 m ² / g and most preferably from 120 to 235 m ² / g, and a CTAB surface area (according to ASTM D 3765) from 30 to 400 m ² / g, preferably from 30 to 330 m ² /g, more preferably from 80 to 300 m ² /g and most preferably from 115 to 200 m ² /g. Such silicas lead z. B. in rubber mixtures for tire treads to particularly good physical properties of the vulcanizates. In addition, advantages in compound processing can result from a reduction in mixing time with the same product properties, which lead to improved productivity. As silicas z. B. both those of the type Ultrasil® VN3 (Flandelsname) from Evonik and highly dispersible Silicic acids, so-called HD silicic acids (e.g. Zeosil® 1165 MP from Solvay), are used.

According to particularly advantageous embodiments of the invention, the rubber mixture contains at least one silica as a filler, preferably in amounts of 30 to 500 phr, particularly preferably 50 to 400 phr, again preferably 80 to 300 phr.

In these amounts, silicic acid is present in particular as the sole or main filler (more than 50% by weight, based on the total amount of filler).

According to further advantageous embodiments of the invention, the rubber mixture contains at least one silica as an additional filler, preferably in amounts of 5 to 100 phr, particularly preferably 5 to 80 phr, again preferably 10 to 60 phr.

Silicic acid is contained in these amounts in particular as a further filler in addition to another main substance, such as in particular a carbon black.

The terms “silicic acid” and “silica” are used synonymously in the context of the present invention.

According to particularly advantageous embodiments 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, very particularly preferably from 5 to 15 phr, of at least one carbon black. In these amounts, carbon black is contained in particular as a further filler in addition to a main filler, such as in particular silica.

According to further advantageous embodiments of the invention, the rubber mixture according to the invention contains 30 to 300 phr, preferably 30 to 200 phr, particularly preferably 40 to 100 phr of at least one carbon black. In these amounts, carbon black is present as the only filler or as the main filler and optionally in combination with silica in the smaller amounts mentioned above. According to a particularly advantageous embodiment of the invention, the rubber mixture contains 5 to 60 phr, particularly preferably 5 to 40 phr, of at least one carbon black and 50 to 300 phr, preferably 80 to 200 phr of at least one silica.

The rubber mixture can also contain other fillers that have a reinforcing effect or do not have a reinforcing effect.

Within the scope of the present invention, the other (non-reinforcing) fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide or rubber gels and fibers (such as, for example, aramid fibers, glass fibers, carbon fibers, cellulose fibers).

Other possibly reinforcing fillers are, for example, carbon nanotubes (carbon nanotubes (CNT) including discrete CNTs, so-called hollow carbon fibers (FICF) and modified CNT containing one or more functional groups such as flydroxy, carboxy and carbonyl groups), graphite and graphene and so-called “carbon-silica dual-phase filier”.

In the context of the present invention, zinc oxide does not belong to the fillers.

Furthermore, the rubber mixture can contain customary additives in customary parts by weight, which are preferably added in at least one basic mixing stage during its production. These additives include a) anti-aging agents known in the prior art, such as e.g. B. 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,2-dihydroquinoline (TMQ), b) activators such as e.g. B. zinc oxide and fatty acids (z. B. stearic acid) and / or other activators such as zinc complexes such as zinc ethylhexanoate, c) Activators and/or agents for binding fillers, in particular carbon black or silicic acid, such as S-(3-aminopropyl)thiosulfuric acid and/or its metal salts (binding to carbon black) and silane coupling agents (binding to silicon dioxide, in particular silicic acid) , d) anti-ozone waxes, e) resins, in particular adhesive resins, f) mastication aids, such as e.g. B. 2,2'-Dibenzamidodiphenyldisulphide (DBD) and g) processing aids, such as in particular fatty acid esters and metal soaps, such as zinc soaps and / or calcium soaps h) plasticizers, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, such as MES (mild extraction solvate ) or RAE (Residual Aromatic Extract) or TDAE (treated distillate aromatic extract), or Rubber-to-Liquid oils (RTL) or Biomass-to-Liquid oils (BTL) preferably with a content of polycyclic aromatics of less than 3 % by weight according to method IP 346 or triglycerides such as e.g. B. rapeseed oil, or facts or hydrocarbon resins or liquid polymers whose average molecular weight (determined by GPC = gel permeation chromatography, based on BS ISO 11344:2004) is between 500 and 20,000 g/mol.

When using mineral oil, this is preferably selected from the group consisting of DAE (Distillated Aromatic Extracts), RAE (Residual Aromatic Extract), TDAE (Treated Distillated Aromatic Extracts), MES (Mild Extracted Solvents) and naphthenic oils.

According to particularly advantageous embodiments, in addition to the compound according to the invention of the formula I), in particular of the formula II), the rubber mixture according to the invention does not contain any aging inhibitors from the group of p-phenylenediamines, in particular those from list a) above. In particular, according to a particularly preferred embodiment, the rubber mixture according to the invention contains from 0 to 0.1 phr, in particular 0 phr, of further aging inhibitors based on p-phenylenediamines, which are 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).

With the preferably very small amounts of 0 to 0.1 phr or particularly preferably 0 phr of p-phenylenediamines and the compound according to the invention contained according to formula I), in particular according to formula II), it is possible to achieve a comparable protective effect with lower toxicity achieve. Here, the compound according to the invention of the formula I), in particular of the formula II), replaces the p-phenylenediamines mentioned which are known in the prior art.

According to further advantageous embodiments of the invention, at least one other of the p-phenylenediamine anti-aging agents mentioned is also present, so that the compound according to the invention only partially replaces the p-phenylenediamines known in the prior art. Flier also achieves the advantage of the invention, just not to the optimum extent.

According to advantageous embodiments, aging inhibitors based on dihydroquinoline, such as TMQ, are present in the rubber mixture in addition to the compound according to the invention of the formula I). The amount of dihydroquinolines present, such as TMQ in particular, is preferably from 0.1 to 3, in particular from 0.5 to 1.5 phr.

Anti-ozone waxes (group d above) are considered separately and, according to preferred embodiments of the invention, are present in the rubber mixture, regardless of whether additional anti-aging agents a) are present.

The silane coupling agents can be of any type known to those skilled in the art.

Furthermore, one or more different silane coupling agents can be used in combination. The rubber mixture can thus contain a mixture of different silanes. The silane coupling agents react with the surface silanol groups of the silicon dioxide, in particular the silicic acid, or other polar groups during the mixing of the rubber or the rubber mixture (in situ) or even before the filler is added to the rubber in the sense of a pretreatment (premodification).

Coupling agents known from the prior art are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group as a leaving group on the silicon atom and which have a group as another functionality which, after cleavage, can undergo a chemical reaction with the double bonds of the polymer. The latter group can be z. Examples are the following chemical groups:

-SCN, -SH, -NH ₂ or -Sx- (where x = 2 to 8).

Thus, as silane coupling agents z. B. 3-mercaptopropyltriethoxysilane, 3-thiocyanato-propyltrimethoxysilane or 3,3'-bis (triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms, such as. B. 3,3'-bis (triethoxysilylpropyl) tetrasulfide (TESPT), the corresponding disulfide (TESPD) or mixtures of the sulfides with 1 to 8 sulfur atoms with different contents of the various sulfides can be used. TESPT can also be added, for example, as a mixture with carbon black (trade name X50S® from Evonik).

Blocked mercaptosilanes, as z. B. are known from WO 99/09036, can be used as a silane coupling agent. Silanes, as described in WO 2008/083241 A1, WO 2008/083242 A1, WO 2008/083243 A1 and WO 2008/083244 A1, can also be used. Can be used e.g. B. silanes under the name NXT in different variants from Momentive, USA, such as in particular 3-octanoylthio-1-propyltriethoxysilane, or those sold under the name VP Si 363® by Evonik Industries.

The proportion of the total amount of further additives is preferably 3 to 150 phr, particularly preferably 3 to 100 phr and very particularly preferably 5 to 80 phr. Zinc oxide (ZnO) can be contained in the abovementioned amounts in the total proportion of the other additives.

This can be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder. The conventionally used zinc oxide usually has a BET surface area of less than 10 m ² /g. However, a zinc oxide with a BET surface area of 10 to 100 m ² /g, such as so-called “nano-zinc oxides”, can also be used.

The rubber mixture according to the invention is preferably used in vulcanized form, in particular in vehicle tires or other vulcanized technical rubber articles.

The terms “vulcanized” and “crosslinked” are used synonymously in the context of the present invention.

The vulcanization of the rubber mixture according to the invention is preferably carried out in the presence of sulfur and/or sulfur donors with the aid of vulcanization accelerators, it being possible for some vulcanization accelerators to also act as sulfur donors. The accelerator is selected from the group consisting of thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthogenate accelerators and guanidine accelerators.

Preferred is the use of a sulfenamide accelerator selected from the group consisting of N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS),

benzothiazyl-2-sulfenmorpholide (MBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS) and guanidine accelerators such as diphenylguanidine (DPG).

All sulfur-donating substances known to those skilled in the art can be used as the sulfur-donating substance.

In addition, vulcanization retarders can be present in the rubber compound. Otherwise, the rubber mixture is preferably prepared by the process customary in the rubber industry, in which a basic mixture with all the components apart from the vulcanization system (e.g. sulfur and substances that influence vulcanization) is first prepared in one or more mixing stages. The finished mixture is produced by adding the vulcanization system in a final mixing stage.

The finished mixture is further processed, e.g. by an extrusion process or calendering, and brought into the appropriate shape.

The rubber mixture according to the invention is particularly suitable for use in vehicle tires, in particular pneumatic vehicle tires. The use in all tire components is conceivable in principle, in particular in an outer component, in particular and preferably in the horn profile, tread strip and/or the sidewall tread strip. In the case of a tread strip with a cap/base construction, the rubber mixture according to the invention is preferably used at least in the cap.

For use in vehicle tires, the mixture is brought into the appropriate form, preferably an outer component, as a ready-to-use mixture before vulcanization and applied in the known manner during the production of the vehicle tire blank.

The rubber mixture according to the invention for use as other body mixture in vehicle tires is produced as already described. The difference lies in the shaping after the extrusion process or the calendering of the mixture. The forms of the still unvulcanized rubber mixture obtained in this way for one or more different body mixtures are then used to build up a green tire.

The rubber mixtures for the inner components of a tire, such as essentially squeegee, inner liner (inner layer), core profile, belt, shoulder, belt profile, carcass, bead reinforcement, bead profile, horn profile and bandage, are referred to as body mixture. The still unvulcanized green tire is then vulcanized.

To use the rubber mixture according to the invention in belts and belts, in particular in conveyor belts, the extruded, still unvulcanized mixture is brought into the appropriate shape and is often provided with reinforcements, e.g. synthetic fibers or steel cords, either at the same time or afterwards. In most cases, this results in a multi-layer structure consisting of one and/or more layers of rubber mixture, one and/or more layers of the same and/or different reinforcements and one or more other layers of the same and/or another rubber mixture.

A further subject of the present invention is a vehicle tire which has the rubber mixture according to the invention containing the compound according to the invention in at least one component.

At least one component of the vulcanized vehicle tire has a vulcanizate of at least one rubber mixture according to the invention. It is known to those skilled in the art that most substances, e.g. B. the contained rubbers are present or can be present in a chemically modified form either after mixing or only after vulcanization.

In the context of the present invention, vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction site vehicles, truck, passenger car and two-wheeler tires.

The vehicle tire according to the invention preferably has the rubber mixture according to the invention in at least one outer component, the outer component preferably being a tread strip, a side wall and/or a horn profile.

The vehicle tire according to the invention can therefore also have the rubber mixture according to the invention containing the compound according to the invention according to formula I), in particular according to formula II), in a plurality of components in an optionally adapted composition. The invention is to be explained in more detail below using exemplary embodiments.

The compound of the formula II) as a preferred embodiment of the compound of the formula I) was prepared in the following manner according to a first synthesis route:

Synthesis of 2-(p-phenylenediamine)-methylbenzoate according to Scheme XI):

xi)

The two starting substances are commercially available.

1.6 g (14.5 mmol, 2.0 eq) of p-phenylenediamine and 1.9 g of 2-iodomethylbenzoate (7.24 mmol, 1.0 eq) were placed in 20 ml of dry dimethyl sulfoxide (DMSO). After the addition of 1.00 g of potassium carbonate (K2CO3) (7.24 mmol, 1.0 eq) and 0.14 g of copper iodide (Cul) (0.72 mmol, 0.1 eq), the mixture was stirred at 80° C. overnight. After the reaction had ended, the solvent was removed by distillation and the residue was taken up in a mixture of ethyl acetate and 5% strength aqueous ammonia. The organic phase was before it was dried over sodium sulfate, once more with 5% ammonia solution, water and sat. saline solution shaken out. The inorganic salts were separated by filtration and the solvent removed in vacuo. The residue was purified by column chromatography on silica gel (dichloromethane (DCM)/methanol (MeOH) 95:5). orange oil; Yield 1.6 g (91% of theory).

¹ H-NMR (nuclear magnetic resonance) (500 MHz, DMSO -d6) d = 9.00 (s,

1H), 7.83 (dd, J = 8.6, 1.7Hz, 1H), 7.29 (ddd, J = 8.6, 7.0, 1.7Hz, 1H), 6.91 (d, J = 8.5Hz, 2H), 6.79 ( dd, J = 8.6, 1.1 Hz, 1H), 6.67 - 6.56 (m, 3H), 5.07 (s, 2H), 3.84 (s, 3H). ¹³ C NMR (126MHz, DMSO-d6) d = 168.7, 150.4, 146.9, 134.9, 128.4, 126.6, 116.0, 115.1, 113.4, 110.0, 52.2.

Synthesis of 2-(/V ¹ -(4-methylpentan-2-yl)-/V ⁴ -p-phenylenediamine)-methyl benzoate according to Scheme XII):

6.80 g (28.1 mmol, 1 eq) of 2-(p-phenylenediamine)methyl benzoate, 1.18 g of palladium on carbon (Pd/C) (5%) (0.2 g to 4.67 mmol substrate) and 50.0 ml_ methyl isobutyl ketone (MIBK) weighed. 20 bar of hydrogen (H2) was then injected and the mixture was stirred at 60° C. for 10 hours. After the reaction had ended, the excess hydrogen was vented and the suspension was filtered through ^Celite® and washed with ethanol. The filtrate was evaporated to dryness and dried in vacuo. The residue was purified by column chromatography on silica gel (cyclohexane/EE (ethyl acetate) 95:5). An orange oil was obtained; Yield 8.20 g (89% of theory).

¹ H NMR (500 MHz, DMSO-de) d = 9.01 (s, 1H), 7.83 (dd, J = 8.1, 1.7 Hz, 1H), 7.30 (ddd, J = 8.7, 7.0, 1.7 Hz, 1 H) , 6.95 (d, J = 8.7 Hz, 2H), 6.81 (dd, J = 8.6, 1.1 Hz, 1 H), 6.66 - 6.56 (m, 3H), 5.32 (d, J = 8.6 Hz, 1 H), 3.84 (s, 3H), 3.44 (dq, J = 8.6, 6.7 Hz, 1H), 1.74 (dt, J = 13.4, 6.7 Hz, 1H), 1.46 (dt, J = 14.0, 7.1 Hz, 1H), 1.27 - 1.16 (m,

1H), 1.09 (d, J = 6.2Hz, 3H), 0.92 (d, J = 6.6Hz, 3H), 0.88 (d, J = 6.6Hz, 3H).

¹³ C NMR (126MHz, DMSO-d6) d = 168.7, 150.4, 146.6, 134.9, 131.6, 127.7, 126.8, 116.0, 113.4, 113.3, 109.9, 52.2, 46.4, 46.0, 25.00, 23.2.00, 23.2.00, 23.2.00

ESI-MS (electrospray ionization mass spectrometry) [M+H] ⁺ = 327. Synthesis of 2-(/V ¹ -(4-methylpentan-2-yl)-/V ⁴ -p-phenylenediamine)-benzoic acid according to Scheme XIII):

XIII)

It became 3.90 g

2-(/V ¹ -(4-Methylpentan-2-yl)-/V ⁴ -p-phenylenediamine)-methyl benzoate (12.0 mmol,

1 eq) in 40 ml_ degassed dioxane and 50 ml_ degassed sodium hydroxide solution (sodium hydroxide, NaOH) (2 molar) heated under reflux overnight. After the reaction reached room temperature (RT), the pH was adjusted to 7 under ice-cooling. It was extracted three times with 2-methyltetrahydrofuran (2-MTHF), the combined organic phases were shaken out with water and saturated (satted) sodium chloride solution and dried over sodium sulfate. A dark green solid was obtained; Yield 3.70 g (99% of theory).

¹ H NMR (500 MHz, DMSO-öe) d = 10.91 (br s, 1H), 7.85 (dd, J = 7.7, 1.8 Hz, 1H), 7.04 (ddd, J = 8.6, 7.0, 1.8 Hz, 1 H), 6.89 (d, J = 8.7 Hz, 2H), 6.81 (dd, J = 8.3, 1.1 Hz, 1H), 6.55 (d, J = 8.7 Hz, 2H), 6.48 (ddd, J = 8.0, 7.1 , 1.2 Hz, 1 H), 5.05 (br s, 1 H), 3.41 (q, J = 6.5 Hz, 1H), 1.74 (dt, J = 13.5, 6.7 Hz, 1H), 1.45 (dt, J = 13.4, 7.1Hz,

1 H), 1.21 (dt, J = 13.5, 6.9 Hz, 1H), 1.08 (d, J = 6.1 Hz, 3H), 0.92 (d, J = 6.7 Hz, 3H), 0.88 (d, J = 6.5 Hz , 3H).

¹³ C NMR (126 MHz, DMSO) d = 172.1, 148.8, 144.9, 132.4, 130.9, 130.8, 124.4, 115.0, 113.5, 111.9, 46.5, 46.2, 25.0, 23.2, 23.1, 21.2.

ESI-MS [M+H] ⁺ = 313. Synthesis of 2-(1,3-dimethylbutylamino)-acridin-9(10/-/)-one (compound according to

Formula II)) according to Scheme XIV):

There were 7.80 g of 2-(/V ¹ -(4-methylpentan-2-yl)-/V ⁴ -p-phenylenediamine)-benzoic acid (25.0 mmol, 1 eq) in 40 ml_ polyphosphoric acid (PPA) for 16 hours at 130 °C stirred. After the reaction was brought to 60°C, the PPA was slowly hydrolyzed by adding water. The solution was then cooled to RT and the pH adjusted to 7. It was extracted three times with 2-MTHF, the combined organic phases with water and sat. Extracted from saline solution and dried over sodium sulfate. The organic salts were removed by filtration and the solvent removed in vacuo. The residue was then purified by column chromatography on silica gel (cyclohexane/EE+1% triethylamine (TEA) or cyclohexane/tetrahydrofuran (THF)+1% TEA). A yellow to bronze colored solid was obtained; Yield 5.30 g (72% of theory).

¹ H NMR (500 MHz, DMSO-öe) d = 11.47 (s, 1 H), 8.19 (dd, J = 8.2, 1.5 Hz, 1 H), 7.62 (ddd, J = 8.4, 6.8, 1.6 Hz, 1 H), 7.47 (d, J = 8.4 Hz, 1 H), 7.37 (d, J = 8.8 Hz, 1 H), 7.24 - 7.09 (m, 3H), 5.48 (d, J = 8.3 Hz, 1 H ), 3.51 (dq, J = 7.8, 6.3 Hz, 1 H), 1.77 (dt, J = 13.4, 6.7 Hz, 1 H), 1.51 (dt, J= 13.9, 7.1 Hz, 1H), 1.26 (dt, J = 13.6, 6.8 Hz, 1H), 1.14 (d, J = 6.2 Hz, 3H), 0.95 (d, J = 6.6 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H).

¹³ C NMR (126 MHz, DMSO) d = 176.4, 143.7, 140.5, 133.2, 132.7, 126.4, 123.8, 122.3, 120.3, 119.8, 118.8, 117.6, 102.9, 46.3, 46.2, 23.1.2, 23.1.2, 23.2.0, 2, 25.2.0, 2

ESI-MS [M+H] ⁺ = 295. Alternative synthesis of 2-(1,3-dimethylbutylamino)-acridin-9(10/-/)-one

(Compound according to formula II)) from

2-(/V ¹ -(4-Methylpentan-2-yl)-p-phenylenediamine)-methylbenzoate according to the scheme

XIV):

It became 4.70 g

2-(/V ¹ -(4-Methylpentan-2-yl)-/V ⁴ -p-phenylenediamine)-methyl benzoate (2.14 mmol,

1 eq) dissolved in 40 ml sulfuric acid (H2SO4) (13.5 M) and stirred at 115°C for 16 hours. After the reaction came to RT, the pH was adjusted to 7 with ice cooling. It was extracted three times with 2-MTHF, the combined organic phases with water and sat. Extracted from saline solution and dried over sodium sulfate. The organic salts were removed by filtration and the solvent removed in vacuo. The residue was then purified by column chromatography on silica gel (cyclohexane/EE+1% TEA or cyclohexane/THF+1% TEA). A yellow to bronze colored solid was obtained; Yield 2.90 g (69% of theory).

ESI-MS [M+H] ⁺ = 295. According to another synthetic route, the compound according to formula II) was prepared in the following way:

First, 2-nitroacridin-9(10/-/)-one was synthesized according to R. Freyer J. Chem. 1963, 4979-5004 - as shown in Scheme Y1): where K2CO3 stands for potassium carbonate and DMF for dimethylformamide.

From there, the synthesis of 2-(1,3-dimethylbutylamino)-acridin-9(10/-/)-one (compound of the formula II) according to Scheme Yll) took place:

0.55 g (2.62 mmol, 1 eq) 2-nitroacridin-9(10H)-one, 0.23 g platinum (5%) (0.4 g on 4.67 mmol substrate) and 20.0 ml_ Methyl isobutyl ketone weighed. 40 bar of hydrogen were then injected and the mixture was stirred at 140° C. for 10 hours. After the reaction had ended, the excess hydrogen was vented and the suspension was filtered through ^Celite® and washed with ethanol. The filtrate was evaporated to dryness and dried in vacuo. The residue was analyzed by LC-MS. The result is shown in Table 1.

The substance can be purified by column chromatography on silica gel (cyclohexane/ethyl acetate 10:1 -> 1:1). Light yellow solid. Table 1

Measurement of the oxidation induction time (OIT, English "oxidation induction time") The compound according to formula II) was measured by measuring the

Oxidation induction time tested under laboratory conditions for its potential protective effect as an anti-aging agent.

For this purpose, the compounds of the formula II) and 6-PPD were each used together with a polymer (liquid synthetic polyisoprene (IR), LIR-50, from Kuraray, weight-average molecular weight distribution Mw=54,000 g/mol,

glass transition temperature Tg = _-63 °C) at a constant temperature (180°C) until oxidation occurred (starting temperature 35°C, heating to 170°C at a heating rate of 20 K/min (Kelvin per minute), heating to 180° C with a heating rate of 1 K/min; purge gas: nitrogen (N2) with a flow rate of 50 mL/min). The sample was kept isothermally under an N2 atmosphere at 180°C for 5 minutes and then switched to an O2 atmosphere (with a flow rate of 50 mL/min).

The oxidation was determined via a peak using DSC (differential scanning calorimetry).

The time in minutes until oxidation was measured. The results are summarized in Table 2 in comparison to the known anti-aging agent 6-PPD.

Table 2

Taking into account the measurement accuracy of ±(plus/minus) 10 minutes, it is found that the compound according to formula II) even achieves a significantly better protective effect, since it takes longer for the polymer to be decomposed by oxygen. The compound according to the invention of the formula I) or formula II) is therefore more environmentally friendly and health-friendly than 6-PPD or other representatives of the substance class, as stated at the outset, and also a better anti-aging agent.

For use in a rubber mixture for vehicle tires, the compound according to the invention according to formula I), for example according to formula II), for example instead of the anti-aging agents known in the prior art, such as 6PPD, 7PPD or IPPD etc., in a manner known to the person skilled in the art in one of the Added mixing stages in the manufacture of the rubber compound.

The compound according to formula II) was then mixed into an exemplary rubber mixture according to the invention, as shown in Table 3. The resulting example according to the invention is marked E1.

As a comparison, a rubber mixture C1 containing 6PPD serves as anti-aging agent instead of the compound of the formula II) with an otherwise identical composition. The amounts in Table 3 are given in units of phr.

The mixture was prepared by the process customary in the rubber industry under customary conditions in three stages in a laboratory mixer 300 milliliters to 3 liters volume, in which initially in the first mixing stage (basic mixing stage) all components except the vulcanization system (sulphur and vulcanization-influencing substances) were mixed for 200 to 600 seconds at 145 to 165 °C, target temperatures of 152 to 157 °C . In the second stage, the mixture from the first stage was mixed again. The ready mix was produced by adding the vulcanization system in the third stage (ready mix stage), with mixing at 90 to 120° C. for 180 to 300 seconds.

Test specimens were produced from all the mixtures by vulcanization according to t95 to t100 (measured on a moving die rheometer according to ASTM D 5289-12/ISO 6502) under pressure at 160° C. to 170° C.

In addition, some of the test specimens of both V1 and E1 were aged (70 °C for 28 days in air).

The following material properties typical of the rubber industry were determined with all test specimens:

• Resilience at room temperature (RT) according to ISO 4662 or ASTM D 1054

• Elongation at break at room temperature (RT), according to DIN 53504

The difference between the values for the non-aged and aged samples was determined for V1 and E1 in each case.

The values obtained for V1 were each normalized to 100% as a reference.

The values obtained for E1 (difference between unaged and aged) are given as performance % in relation to this respective V1 reference, with values greater than 100% being advantageous.

As can be seen from Table 3, the compound of the formula II) according to the invention as a representative of the compound of the formula I) results in improved protection against aging because of important properties such as elongation at break and the rebound resilience at E1 after aging are each at a higher level than at V1.

Table 3

Claims

patent claims

1. Compound according to formula I): wherein R ¹ is selected from the group consisting of xi) aromatic residues, the aromatic residues optionally having substituents selected from the group consisting of halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether radicals, and xii) linear, branched and cyclic aliphatic C4 to C12 radicals, and xiii) combinations of aromatic and aliphatic C1 to C12 radicals; and wherein the radicals R ² and R ³ independently can be the same or different and are selected from the group consisting of linear, branched and cyclic, saturated and unsaturated, aliphatic C to C-12 radicals which optionally contain one or more halogen - Carry substituents, aryl radicals, which optionally carry one or more halogen substituents, and halogen radicals, with fluorine, bromine and chlorine being preferred, cyano radicals, ester radicals,

ketone residues, ether residues and thioether residues, and where n has the value 0 or 1 or 2 or 3 or 4, the residues R ³ being 2 or 3 or 4 independently of one another the same or different, and where m has the value 0 or 1 or 2 or 3, where the radicals R ² are independently identical or different when m is 2 or 3.

2. A compound according to claim 1, characterized in that n is 0 (zero).

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

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

5. A compound according to any one of the preceding claims, characterized in that R ¹ is a branched alkyl radical having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms.

6. Compound according to any one of the preceding claims, characterized in that R ¹ is selected from 1, 3-dimethylbutyl and cyclohexyl radicals, where R ¹ is preferably a 1, 3-dimethylbutyl radical.

7. A compound according to any one of the preceding claims, characterized in that it has the structure according to formula II):

8. Use of the compound according to any one of claims 1 to 7 as

Anti-aging agents, in particular in vehicle tires or technical rubber articles, such as in particular an air spring, a bellows, conveyor belt, belt, strap, hose, rubber band, profile, a seal, a membrane, tactile sensors for medical applications or robot applications, or a shoe sole or parts thereof, and/or oils and/or lubricants.

9. Use of the compound according to any one of claims 1 to 7 as a dye in fibers and/or polymers and/or paper and/or in (coating) paints and varnishes.

10. Process for preparing the compound of the formula I), which comprises the following process steps: a) Provision of the compounds of the formula A) and B) b) Reaction of the compounds A) and B) with one another in the presence of a base and a catalyst, the compound of the formula C) being obtained: c) Reaction of the compound of the formula C) with hydrogen or a hydrogenating reagent, in particular a hydride, and a ketone or aldehyde to form the compound of the formula D): d) optional conversion of the compound according to formula D) to the compound according to formula E): e) Reaction of the compound of the formula D) or E) with an acid to give the compound of the formula I): wherein R ¹ is selected from the group consisting of xi) aromatic residues, the aromatic residues optionally having substituents selected from the group consisting of flalogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether radicals, and xii) linear, branched and cyclic aliphatic, in particular C4 to C12 radicals, and xiii) combinations of aromatic and aliphatic C1 to C12 radicals; and wherein the radicals R ² and R ³ can independently be the same or different and are selected from the group consisting of linear, branched and cyclic, saturated and unsaturated, aliphatic C to C-12 radicals, which optionally contain one or more Flalogen -Carry substituents, aryl radicals, which optionally carry one or more Flalogen substituents, and Flalogen radicals, fluorine, bromine and chlorine being preferred, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether radicals radicals, and where n has the value 0 or 1 or 2 or 3 or 4, where the radicals R ³ are independently identical or different when n is 2 or 3 or 4, and where m has the value 0 or 1 or 2 or 3, where the radicals R ² are independently identical or different when m is 2 or 3.

11. The method according to claim 10, characterized in that the reaction in step c) with hydrogen and the aldehyde or ketone, preferably ketone, takes place using a hydrogenation catalyst and at a temperature of 120 to 150 ° C and hydrogen at a pressure of 35 is pressed up to 45 bar and the reaction takes place in an autoclave or in another pressure reactor.

12. A rubber mixture containing the compound according to any one of claims 1 to 7, wherein the rubber mixture preferably contains at least one diene rubber, which is particularly preferably 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.

13. A vehicle tire which has the rubber mixture according to claim 12 in at least one component, preferably in at least one outer component, the outer component preferably being a tread strip, a side wall and/or a horn profile.