Compound, rubber blend containing said compound, vehicle tire containing said rubber blend as at least one component, process for producing said compound, and use of said compound as ageing stabilizer and / or antiozonant and / or dye

Abstract

The present invention relates to a compound, a rubber blend containing said compound, a vehicle tire comprising at least one component of this rubber blend, a process for the preparation of the compound and the use of the compound as an ageing protectant and / or antiozonant and / or dye. 1 xi) aromatic groups, which optionally have a substituent 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-C 12 xiii) aromatic and aliphatic C1-C 12 In one embodiment, the aryl group is selected from the group consisting of a aryl group and a aryl group. TIFF2024529394000029.tif47170

Description

[Technical Field]

[0001] The present invention relates to a compound, a rubber mixture containing the compound, a vehicle tire comprising the rubber mixture in at least one component, a process for producing the compound, and the use of the compound as an ageing stabilizer and / or antiozonant and / or dye. [Background technology]

[0002] Vehicle tires and technical rubber articles are known to employ polymeric materials, particularly rubber.

[0003] During prolonged storage and, particularly, during intended use, which is often at high temperatures, natural rubber and synthetic polymers (such as IR, BR, SBR, 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 until subsequent hardening of the material occurs.

[0004] Aging stabilizers therefore play a crucial role in the durability of vehicle tires and other technical rubber articles.

[0005] Known ageing stabilizers 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).

[0006] These molecules are capable of reacting with oxygen or ozone or with the free radicals formed, such as alkyl, alkoxy and alkylperoxy radicals, thereby scavenging them and thus protecting the rubber etc. from further oxidation reactions.

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

[0008] Aging stabilizers that specifically react with ozone to achieve its scavenging are also called "antiozonants." Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to provide novel compounds that can be used in particular as ageing stabilizers for vehicle tires or other industrial rubber articles, and that are less potentially hazardous, in particular in combination with sufficient solubility in the respective matrix, for example in particular in polymers, with the intention of preventing the tendency to blooming while maintaining optimal protection from oxygen and ozone and reducing the hazard to health. [Means for solving the problem]

[0010] This object is achieved by the compounds according to the invention as claimed in claim 1, by rubber mixtures according to the invention which contain the compounds, and by vehicle tyres according to the invention which contain rubber mixtures according to the invention in at least one of their components.

[0011] This object is further achieved by using the compounds as ageing stabilizers and / or antiozonants.

[0012] The compounds according to claim 1 may further be used as dyes.

[0013] This object is further achieved by the process according to the invention for preparing the compounds according to the invention.

[0014] The compound as claimed in claim 1 has the general formula I): [ka] [In the formula, R 1 teeth, xi) an aromatic group, wherein the aromatic group optionally bears 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 C4-C 12 xiii) aromatic and aliphatic C1-C groups 12 Combination with groups is selected from the group consisting of In the formula, the group R 2 and R 3 are, independently of one another, the same or different, linear, branched and cyclic, saturated and unsaturated, aliphatic C1-C, optionally bearing one or more halogen substituents; 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, wherein n takes the value 0 or 1 or 2 or 3 or 4, and when n is 2 or 3 or 4, the group R 3 are, independently of one another, identical or different, where m takes the value 0 or 1 or 2 or 3, and where m is 2 or 3, the group R 2 are, independently of each other, identical or different] It has.

[0015] R 1 benzyl and linear, branched and cyclic aliphatic C4-C 12 is selected from the group consisting of In the formula, R 3 is linear, branched and cyclic aliphatic C1-C 12 groups and aryl groups, cyano groups, halogen groups (wherein fluorine, bromine and chlorine are preferred), ether groups and thioether groups, wherein n has a value of 0 or 1 or 2 or 3 or 4, and when n is 2 or 3 or 4, the group R 3 are, independently of one another, identical or different, In the formula, R 2 is linear, branched and cyclic aliphatic C1-C 12groups, and aryl groups, cyano groups, halogen groups (wherein fluorine, bromine and chlorine are preferred), ether groups and thioether groups, In the formula, m takes the value 0 or 1 or 2 or 3, and when m is 2 or 3, the group R 3 are, independently of each other, identical or different This is preferable.

[0016] When n is 0 (zero), 1, 2, or 3 in each case, the hydrogen atom is R 3 It will be apparent to one skilled in the art that m is bonded to the corresponding carbon atom of the benzene ring instead of m. Similarly, when m is 0 or 1 or 2, all remaining free positions on the benzene ring of the structure are hydrogen atoms.

[0017] (R 2 ) m and (R 3 ) n and R 1 It will likewise be apparent to those skilled in the art that the representation of the HN bond should be understood as meaning that these groups can each be located at any position on the respective benzene ring, except, of course, that two or more cannot be at the same position at the same time, as would already be precluded by the tetravalency of the carbon atoms of the benzene ring.

[0018] In the context of the present invention, the class "C4-C 12 The reference to a "radical" should be understood to mean a radical having 4 to 12 carbon atoms. Regardless of this, "C1" is also used to describe the position of the most highly oxidized carbon atom / highest priority carbon atom according to the Cahn-Ingold-Prelog (CIP) rules. What is meant in each context will be clear to those skilled in the art.

[0019] The compounds according to the present invention are acridinone derivatives and exhibit lower potential hazards compared to known aniline-based aging stabilizers (potential cleavage products of 6-PPD). Comparison of the safety data sheets of the basic aniline and acridinone reveals that, unlike aniline, acridinone is neither genotoxic nor mutagenic. This is a crucial advantage, particularly in technical applications such as vehicle tires or other rubber products, where rubber components may be liberated by wear or other degradation processes.

[0020] The compounds according to the invention also have an improved protective effect against oxidation and thus ageing, compared to 6-PPD, especially with respect to polymers. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention includes all advantageous embodiments, particularly those reflected in the claims. The present invention also includes embodiments resulting from combinations of different features with different priorities relative to these features, 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 that is, for example, described as "particularly preferred."

[0022] 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, optionally bearing one or more halogen substituents. 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.

[0023] Enumerated groups R 2 and R 3 may in particular already be attached to the respective benzene ring / precursor thereof by the selection of suitable starting materials.

[0024] Preferably, n is 0 (zero).

[0025] It is preferred if m is 0 (zero).

[0026] Radical R 1 teeth, xi) an aromatic radical, which may have a substituent selected from the group consisting of a halogen radical, a cyano radical, an ester radical, a ketone radical, an ether radical, and a thioether radical; and xii) linear, branched and cyclic aliphatic C3-C 12 Radicals, especially C4-C 12 radicals, and xiii) aromatic and aliphatic C1-C 12 The radicals are selected from the group consisting of:

[0027] An aromatic radical from subgroup xi) is, for example, preferably a phenyl radical.

[0028] The aromatic radicals of subgroup xi) may bear substituents.

[0029] As mentioned above, these are selected from the group consisting of halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals and thioether radicals.

[0030] It is preferred if the substituent is selected from the group consisting of an ester radical, a ketone radical, an ether radical and a thioether radical.

[0031] In a preferred embodiment, the aromatic radical is unsubstituted at the two carbon atoms adjacent to the C1 atom, i.e., the carbon atom bonded to the N atom. Therefore, in the case of a benzene ring as the basic structure, it is preferred that there is no substituent at the ortho position relative to the N atom.

[0032] In a further preferred embodiment, the aromatic radicals of subgroup xi) are unsubstituted.

[0033] R 1 is preferably bonded to the nitrogen atom (N) via a tertiary carbon atom. Therefore, the C1 atom is preferably a tertiary carbon atom.

[0034] In the context of the present invention, the term "tertiary carbon atom" should be understood to mean a carbon atom that is bonded to only one hydrogen atom.

[0035] 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.

[0036] The mixed aromatic and aliphatic radicals of subgroup xiii) are, for example, preferably selected from the group consisting of benzyl and 1-phenylalkyl radicals having a total of 7 to 18 carbon atoms, in particular benzyl and 1-phenylethyl radicals, with 1-phenylalkyl radicals, in particular 1-phenylethyl, being particularly preferred for the tertiary carbon atom.

[0037] In a further advantageous embodiment, R 1 is a branched or cyclic alkyl radical having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, where R 1 is particularly preferably selected from the 1,3-dimethylbutyl radical and the cyclohexyl radical, where R 1 is very particularly preferably the 1,3-dimethylbutyl radical.

[0038] This achieves particularly good solubility in rubber mixtures for vehicle tires and other industrial rubber articles.

[0039] In a preferred embodiment, the compound has formula II: [ka] It has the following structure.

[0040] The compounds of formula II) indeed make it possible to achieve further improvements in protection against oxidation and therefore aging, especially in polymers, and at the same time, as mentioned above, the compounds of formula II) are significantly less harmful to health than, for example, 6-PPD or other representatives of this substance class.

[0041] Therefore, compared to 6-PPD, the compound of formula II) is a better and at the same time less harmful to health and environmentally friendly ageing stabilizer.

[0042] The compounds of the invention of formula I), formula II) and all the above mentioned are particularly suitable as ageing stabilizers and / or antiozonants in vehicle tyres and / or technical rubber articles, such as air springs, bellows, conveyor belts, belts, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical applications or robotics, or shoe soles or parts thereof, and / or oils and / or lubricants.

[0043] The present invention therefore further provides the use of the compounds according to the invention as ageing stabilizers and / or antiozonants in vehicle tyres and / or industrial rubber articles, in particular air springs, bellows, conveyor belts, belts, drive belts, hoses, rubber bands, profiles, seals, membranes, tactile sensors for medical or robotic applications, or shoe soles or parts thereof, and / or oils and / or lubricants.

[0044] To use the compounds of Formula I), Formula II), and all of the foregoing in the listed articles or materials, the compounds are used in compositions and incorporated into the compositions.

[0045] In vehicle tires or other industrial rubber articles, the composition is especially present in a rubber mix.

[0046] The present invention further provides the use of the compounds of formula I), formula II) and all of the above inventive compounds as dyes in fibres and / or polymers and / or paper and / or (decorative) paints and coatings.

[0047] A further aspect of the present invention is a method comprising the steps of: a) Formulas A) and B) [ka] providing a compound of formula (I); b) reacting compounds A) and B) with each other in the presence of a base and a catalyst to form a compound of formula C): [ka] obtaining a compound of formula (I); c) reacting a compound of formula C) with hydrogen or a hydrogenation reagent, in particular a hydride, and a ketone or aldehyde (R 1 =O) to form the compound D): [ka] obtaining a compound of formula (I); d) optionally reacting a compound of formula D) to form a compound of formula E): [ka] obtaining a compound of formula (I); e) reacting a compound of formula D) or E) with an acid to form a compound of formula I): [ka] A step of obtaining a compound of A method for preparing a compound of formula I comprising:

[0048] All of the foregoing are groups R 1 , R 2 , and R 3 and applies to the indices m and n.

[0049] The base in step b) is preferably selected from organic and inorganic bases, the inorganic bases being preferably selected from the group consisting of potassium carbonate, potassium phosphate, sodium carbonate, sodium phosphate, cesium carbonate.

[0050] The organic base is preferably selected from the group consisting of sodium tert-butoxide, potassium tert-butoxide.

[0051] The catalyst in step b) is preferably a catalyst which catalyzes via "copper coupling", such as, in particular, copper iodide.

[0052] Copper coupling preferably uses an inorganic base such as copper iodide as a catalyst in conjunction with the base potassium carbonate.

[0053] The catalyst optionally comprises a monodentate or polydentate ligand, particularly a monodentate or polydentate phosphine ligand, also referred to as "palladium coupling." Suitable catalysts include, in particular and for example, triphenylphosphine and binaphthylphosphine (BINAP).

[0054] Copper coupling can use either inorganic or organic bases.

[0055] "Hydrogenation reagent" should be understood to mean a compound that brings about hydrogenation. Such reagents include hydrides, in particular metal hydrides, as known to those skilled in the art.

[0056] Suitable hydrides include, for example, sodium borohydride.

[0057] In the context of the present invention, hydrogen is explicitly mentioned as an alternative and is therefore not additionally listed under "hydrogenation reagents". Nevertheless, it will be understood that the term "hydrogenation reagents" encompasses all reagents that form hydrogen to perform in situ hydrogenation.

[0058] It is preferred if the reaction in step c) is carried out with hydrogen (H2) and a ketone or aldehyde, preferably a ketone, using a hydrogenation catalyst and preferably at a temperature of 50-70°C, in particular for example 60°C.

[0059] The reaction mixture is subjected to hydrogen at a pressure of 15 to 25 bar, in particular for example 20 bar, and then preferably stirred for 1 to 20 hours, preferably 8 to 13 hours, in particular for example 10 hours.

[0060] In step c) the ketone is then reacted with the group R 1 in the case of an aldehyde, it is therefore an aldehyde derivative.

[0061] For simplicity, the group R 1 is the moiety remaining on the nitrogen atom after reaction with the aldehyde or ketone, and is therefore represented by the abbreviated formula R 1 =O is used for aldehydes or ketones.

[0062] The ketone methyl isobutyl ketone is preferably used here.

[0063] The reaction with hydrogen in step c) is preferably carried out in a vessel suitable for relatively high pressures, such as in particular in an autoclave or another pressure reactor.

[0064] The solvent in step c) 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 a reactant in stoichiometric amounts.

[0065] It is preferable to use a ketone or an aldehyde, particularly preferably a ketone, in liquid form as solvent, which makes it possible to avoid additional substances such as toluene or xylene.

[0066] The process step in which the reaction with hydrogen is carried out is preferably carried out using a suitable catalyst, which is referred to in the context of the present invention as a "hydrogenation catalyst".

[0067] 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).

[0068] Additionally, other known catalysts such as Raney nickel or copper chromite may also be used.

[0069] The reaction with a base is optional. The compound of formula D) can also be reacted directly with an acid to give the target compound of formula I).

[0070] The acid used is especially and preferably sulfuric acid (H2SO4).

[0071] However, the reaction according to step d) is preferably carried out first.

[0072] This makes it possible to achieve higher yields of the target compound of formula I).

[0073] The reaction of compounds of formula D) to give compounds of formula E) is an ester cleavage, which is preferably carried out with a suitable reagent therefor, in particular a base, such as sodium hydroxide (NaOH), or an acid, such as concentrated hydrochloric acid (concentrated HCl).

[0074] The reaction in step d) is preferably heated under reflux for several hours, preferably for 4 to 12 hours, particularly preferably for 6 to 10 hours, for example for 8 hours (overnight), and then cooled.

[0075] The pH is then adjusted to 6.8 to 7.2, especially 7, preferably with ice cooling.

[0076] This is followed by extraction with a solvent. It is preferred to use 2-methyltetrahydrofuran (2-MTHF) and to carry out the extraction two or more times, especially three times. The use of 2-methyltetrahydrofuran (2-MTHF) achieves a particularly high yield of the intermediate of formula E).

[0077] If step d) has been carried out previously, the reaction of the compound of formula E) is carried out with an acid, for example and preferably polyphosphoric acid (PPA).

[0078] The reaction in step e) is preferably carried out at a temperature of 120°C to 140°C, for example 130°C. The mixture is then preferably first cooled to a temperature of 50°C to 70°C, and the unreacted acid is hydrolyzed with water. The mixture is then preferably further cooled to room temperature. The pH is then adjusted to 6.8 to 7.2, especially 7. This results in a particularly high yield of the target compound of formula I).

[0079] This is followed by extraction with a solvent. It is preferred to use 2-methyltetrahydrofuran (2-MTHF) and to perform the extraction two or more times, especially two times. The use of 2-methyltetrahydrofuran (2-MTHF) also achieves particularly high yields of the target compound.

[0080] The present invention further comprises at least the following process steps: a1) Formula A1) [ka] [wherein the above-mentioned formula is a group R 2 , R 3 and indices m and n, and X is a halogen, in particular fluorine (F), chlorine (Cl) or bromine (Br). providing a compound of formula (I); b1) Reacting the compound of formula A1) with a base, in particular potassium carbonate (K2CO3), to give the compound of formula B1): [ka] obtaining a compound of formula (I); c1) The compound of formula B1) is reacted with hydrogen or a hydrogenation reagent, in particular a hydride, and a ketone or aldehyde (R 1 =O) to form a compound of formula I): [ka] A step of obtaining a compound of Further methods for preparing compounds of formula I) are provided, including:

[0081] The base in step b1) is preferably a strong base, such as potassium carbonate (K2CO3) or potassium phosphate (K3PO4). It is particularly preferred to use potassium carbonate (K2CO3).

[0082] The reaction according to step b1) is preferably carried out in a polar solvent, in particular dimethylformamide (DMF) or dimethylsulfoxide (DMSO). Dimethylformamide (DMF) is particularly preferably used.

[0083] The reaction in step c1) is carried out with hydrogen and a ketone or aldehyde, preferably a ketone, using a hydrogenation catalyst and preferably at a temperature of 120-150°C, in particular for example 140°C.

[0084] It is preferred if the reaction mixture is subjected to hydrogen at a pressure of 35 to 45 bar, in particular for example 40 bar, and then preferably stirred for 1 to 20 hours, preferably 8 to 13 hours, in particular for example 10 hours.

[0085] In step c) the ketone is reacted with the following radical R 1 In the case of an aldehyde, it is therefore an aldehyde derivative.

[0086] For simplicity, the radical R 1 is the moiety remaining on the nitrogen atom after reaction with an aldehyde or ketone, hence the simplified formula R 1 =O is used for aldehydes or ketones.

[0087] Preferably, the ketone methyl isobutyl ketone is used here.

[0088] The process step in which the reaction with hydrogen is carried out is preferably carried out using a suitable catalyst, which is referred to in the context of the present invention as a "hydrogenation catalyst".

[0089] 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).

[0090] Additionally, other known catalysts such as Raney nickel or copper chromite may also be used.

[0091] The solvent in step c1) 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 in stoichiometric amounts as a reactant.

[0092] It is preferable to use as solvent a ketone or an aldehyde in liquid form, particularly preferably a ketone, which makes it possible to eject additional substances such as toluene or xylene.

[0093] The reaction product of the above process according to the invention is in particular a substance mixture comprising a compound of formula I), wherein step c1) or e) is preferably followed by purification, for example by column chromatography, for example on silica gel.

[0094] As mentioned above, the present invention further provides a rubber mixture.

[0095] The rubber mixtures according to the invention contain compounds of formula I), in particular of formula II). They can in principle be any rubber mixture in which the novel inventive compounds, in particular of formula I), in particular of formula II), act as ageing stabilizers and / or antiozonants with low toxicity.

[0096] The rubber mixtures of the present invention contain at least one rubber.

[0097] It is preferred if the rubber mixtures according to the invention contain 0.1 to 10 phr, particularly preferably 0.1 to 7 phr, very particularly preferably 1 to 6 phr of compounds of the formula I), in particular of the formula II).

[0098] The unit "phr" (parts per hundred parts by weight of rubber) used in this document is the conventional indication of quantities for mixture formulations in the rubber industry. The dosage of parts by weight of individual substances is used in this document to refer to all high molecular weight (M) rubbers present in the mixture. w based on 100 parts by weight of the total mass of rubber (whose molecular weight is greater than 20,000 g / mol).

[0099] In an advantageous embodiment of the invention, the rubber mixture according to the invention contains at least one diene rubber.

[0100] Thus, the rubber mixture may contain a diene rubber or a mixture of two or more different diene rubbers.

[0101] Diene rubbers are rubbers formed by polymerizing or copolymerizing dienes and / or cycloalkenes and therefore have C=C double bonds in either the backbone or in side groups.

[0102] 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 wThe rubber is selected from the group consisting of liquid rubber having a modulus of more 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.

[0103] Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber and / or ethylene-propylene-diene rubber are used in particular in the manufacture of technical rubber articles, such as belts, drive belts and hoses and / or shoe soles, etc. Mixture compositions known to those skilled in the art for these rubbers are preferably employed, which are specific in terms of fillers, plasticizers, vulcanization systems and additives.

[0104] 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 having a cis-1,4 ratio of more than 90% by weight. First, such polyisoprene can be obtained by stereospecific polymerization in solution with a Ziegler-Natta catalyst or using finely divided lithium alkyls. Second, 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.

[0105] Mixtures of one or more natural polyisoprenes with one or more synthetic polyisoprenes are also contemplated.

[0106] In the context of the present invention, the term "natural rubber" should be understood to mean natural rubber obtainable from the Hevea rubber tree and from "non-Hevea" sources, such as the guayule shrub and dandelions, such as TKS (Taraxacum kok-saghyz; Russian dandelion).

[0107] When the rubber mixture of the present invention contains butadiene rubber (i.e., BR, polybutadiene), it may be of any type known to those skilled in the art. These include those called high-cis and low-cis types, where polybutadiene having a cis content of 90% by weight or more is called high-cis type, and polybutadiene having a cis content of less than 90% by weight is called low-cis type. An example of low-cis polybutadiene is Li-BR (lithium-catalyzed butadiene rubber) having 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.

[0108] The polybutadiene employed may be end-modified and / or functionalized along the polymer chain. The modification may be selected from hydroxyl and / or ethoxy and / or epoxy and / or siloxane and / or amino and / or aminosiloxane and / or carboxyl and / or phthalocyanine and / or silane-sulfide modifications. However, further modifications known to those skilled in the art, also referred to as functionalization, are also useful. Metal atoms may be components of such functionalization.

[0109] If at least one styrene-butadiene rubber (styrene-butadiene copolymer) is present in the rubber mixture, it may be selected from solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized styrene-butadiene rubber (ESBR), and it is also possible to employ 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.

[0110] The styrene-butadiene copolymers used may be end-group-modified and / or functionalized along the polymer chain by the modifications and functionalizations mentioned above for polybutadiene.

[0111] 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.

[0112] 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).

[0113] In a particularly advantageous embodiment of the invention, the rubber mixture comprises at least one natural polyisoprene (NR) and / or synthetic polyisoprene (IR) in an amount of preferably 50 to 100 phr, in one particularly advantageous embodiment of the invention in an amount of 80 to 100 phr, very particularly preferably 95 to 100 phr, then preferably 100 phr. Such rubber mixtures exhibit in particular optimized tear and wear properties combined with good processability and reversion stability.

[0114] If the rubber mixture contains less than 100 phr of NR and / or IR, the rubber mixture preferably contains as further rubber 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).

[0115] In a further particularly advantageous embodiment of the present invention, the rubber mixture comprises at least one natural polyisoprene (NR), preferably in an amount of 5 to 55 phr, and in one particularly advantageous embodiment of the present invention in an amount of 5 to 25 phr, very particularly preferably 5 to 20 phr. Such rubber mixtures exhibit particularly good processability and reversion stability, as well as optimized tear properties and optimum rolling resistance characteristics.

[0116] 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, particularly preferably 10 to 50 phr, and in a particularly advantageous embodiment of the invention, 15 to 40 phr, whereby particularly good tear and wear properties and optimal braking characteristics of the rubber mixture according to the invention are achieved.

[0117] 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, particularly preferably 30 to 80 phr, and in one particularly advantageous embodiment of the present invention, 50 to 70 phr. This achieves particularly good rolling resistance properties of the rubber mixture according to the present invention. In a particularly advantageous embodiment of the present invention, the SSBR is employed in combination with at least one further rubber in order to achieve an optimal and balanced property profile.

[0118] It is preferred if the rubber mixture contains at least one filler, preferably in an amount of 30 to 500 phr, particularly preferably 50 to 400 phr, then preferably 80 to 300 phr.

[0119] 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.

[0120] Suitable carbon blacks include any carbon black type 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.

[0121] The carbon black preferably has an iodine number (also known as iodine adsorption) according to ASTM D1510 of 30 to 250 g / kg, preferably 30 to 180 g / kg, particularly preferably 40 to 180 g / kg, and even more particularly preferably 40 to 130 g / kg, and a DBP value (DBP) according to ASTM D2414 of 30 to 200 ml / 100 g, preferably 70 to 200 ml / 100 g, and particularly preferably 90 to 200 ml / 100 g.

[0122] The DBP value according to ASTM D2414 determines the specific absorption volume of carbon black or light colored filler relative to dibutyl phthalate.

[0123] 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.

[0124] 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 type N 339 carbon black.

[0125] The silicon dioxide is preferably amorphous silicon dioxide, for example precipitated silica, also known as precipitated silicon dioxide. However, it is also possible to use, for example, pyrogenic silicon dioxide.

[0126] However, it is particularly preferred to use finely divided precipitated silicas having a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) of 35 to 400 m / g, preferably 35 to 350 m / g, more preferably 85 to 320 m / g, and most preferably 120 to 235 m / g, and a CTAB surface area (according to ASTM D 3765) of 30 to 400 m / g, preferably 30 to 330 m / g, more preferably 80 to 300 m / g, and most preferably 115 to 200 m / g. Such silicas, for example in rubber mixtures for tire treads, result in particularly good physical properties of the vulcanized rubber. Advantages in the processing of the mixture due to reduced mixing times can also be obtained while maintaining the same product properties, leading to improved productivity. The silica used can therefore be, for example, Ultrasil® VN3 type (trade name) manufactured by Evonik, or a highly disperse silica known as HD silica (for example Zeosil® 1165MP manufactured by Solvay).

[0127] 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, particularly preferably 50 to 400 phr, then preferably 80 to 300 phr.

[0128] In these amounts, silica is especially present as the sole or primary filler (greater than 50% by weight based on the total amount of filler).

[0129] In a further advantageous embodiment of the invention, the rubber mixture contains at least one silica as further filler, preferably in an amount of 5 to 100 phr, particularly preferably 5 to 80 phr, then preferably 10 to 60 phr.

[0130] In these amounts, the silica is present especially as an additional filler in addition to other primary fillers such as carbon black.

[0131] The terms "silicic acid" and "silica" are used synonymously in the context of the present invention.

[0132] In a particularly advantageous embodiment of the invention, the rubber mixture according to the invention contains 0.1 to 60 phr, preferably 3 to 40 phr, particularly preferably 5 to 30 phr and very particularly preferably 5 to 15 phr of at least one carbon black. In these amounts, the carbon black is in particular present as a further filler in addition to the main filler, in particular silica.

[0133] 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, optionally in combination with silica in the lower limit amounts mentioned above.

[0134] In 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.

[0135] The rubber mixture may further contain further fillers, reinforcing or non-reinforcing.

[0136] In the context of the present invention, further (non-reinforcing) fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide, or rubber gels and fibers (e.g. aramid fibers, glass fibers, carbon fibers, cellulose fibers).

[0137] Further optionally, the reinforcing filler is carbon nanotube (CNT), graphite and graphene, including, for example, discrete CNT, so-called hollow carbon fibers (HCF), and modified CNT containing one or more functional groups such as hydroxyl, carboxyl, and carbonyl groups, and so-called "carbon-silica dual-phase fillers."

[0138] In the context of the present invention, zinc oxide is not included in the filler.

[0139] 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 (carbon black binding) and silane coupling agents (silica binding); d) antiozonant waxes; e) resins, especially tackifying resins; f) mastication aids, such as 2,2'-dibenzamidodiphenyl disulfide (DBD), and g) processing aids, in particular fatty acid esters and metal soaps, for example zinc soap and / or calcium soap, h) plasticizers, such as in particular aromatic, naphthenic or paraffinic mineral oil plasticizers, for example MES (Mild Extraction Solvates), or RAE (Residual Aromatic Extract), or TDAE (Treatment Distillate Aromatic Extract), which preferably have a content of polycyclic aromatic compounds of less than 3% by weight according to method IP 346, or rubber to liquefaction (RTL) oils or biomass to liquefaction (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.

[0140] 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 (Mild Extraction Solvate), and naphthenic oil.

[0141] In a particularly advantageous embodiment, the rubber mixture according to the invention does not contain, in addition to the inventive compound of formula I), in particular of formula II), any 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, of a further ageing stabilizer based on p-phenylenediamine, preferably selected from the group 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).

[0142] The presence of very small amounts of p-phenylenediamine, preferably 0 to 0.1 phr, particularly preferably 0 phr, as well as the compounds of formula I), in particular formula II), according to the invention makes it possible to achieve the same protective effect with lower toxicity.The compounds of formula I), in particular formula II), according to the invention, replace the listed p-phenylenediamines known in the prior art.

[0143] In a further advantageous embodiment of the present invention, at least one further representative of the listed p-phenylenediamine aging stabilizers is present, so that the compounds according to the invention only partially replace the p-phenylenediamines known in the prior art, which also achieve the advantages according to the invention, but only to a less than optimal extent.

[0144] 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 0.1 to 3, in particular 0.5 to 1.5 phr.

[0145] 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 additional ageing stabilizers a) are present or not.

[0146] The silane coupling agent may be of any type known to those skilled in the art.

[0147] 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.

[0148] 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 pre-treatment (pre-modification) situations, even before the addition of filler to the rubber.

[0149] Coupling agents known from the prior art are bifunctional organosilanes that have at least one alkoxy, cycloalkoxy or phenoxy group as a leaving group on the silicon atom and other functional groups that, possibly after cleavage, are capable of undergoing chemical reaction with the double bonds of the polymer. The latter groups can include, for example, the following chemical groups: -SCN, -SH, -NH2 or -S x -(where x=2~8).

[0150] Suitable silane coupling agents include, 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 various sulfides of different contents. TESPT can also be added, for example, as a mixture with industrial carbon black (trade name X50S®, manufactured by Evonik).

[0151] For example, blocked mercaptosilanes, such as those known from WO 99 / 09036, can also be used as silane coupling agents. Silanes described in WO 2008 / 083241A1, WO 2008 / 083242A1, WO 2008 / 083243A1, and WO 2008 / 083244A1 can also be used. Usable silanes include, for example, 3-octanoylthio-1-propyltriethoxysilane, sold in many varieties by Momentive USA under the name NXT, or VP Si 363®, sold by Evonik Industries.

[0152] The total proportion of further additives is preferably 3 to 150 phr, more preferably 3 to 100 phr, most preferably 5 to 80 phr.

[0153] Zinc oxide (ZnO) may be included in the overall proportion of further additives in the amounts mentioned above.

[0154] This can be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder. Conventionally used zinc oxides usually have a BET specific surface area of ​​less than 10 m / g. However, it is also possible to use zinc oxides with a BET surface area of ​​10 to 100 m / g, such as so-called "nano zinc oxide."

[0155] The rubber mixtures of the present invention are preferably used in vulcanized form, especially for vehicle tires or other vulcanized industrial rubber articles.

[0156] The terms "vulcanization" and "crosslinking" are used synonymously in the context of the present invention.

[0157] The vulcanization of the rubber mixtures 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.

[0158] It is preferred to use a sulfenamide accelerator selected from N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazyl-2-sulfen morpholide (MBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and guanidine accelerators such as diphenylguanidine (DPG).

[0159] The sulfur donor material used can be any sulfur donor material known to those skilled in the art.

[0160] Vulcanization retarders may also be present in the rubber mixture.

[0161] In other cases, the preparation of the rubber mixtures according to the invention is preferably carried out by a process customary in the rubber industry, which involves first preparing a primary mixture in one or more mixing stages, which contains all the components except the vulcanization system (e.g., sulfur and vulcanization-affecting substances), and the final mixture is produced by adding the vulcanization system in the final mixing stage.

[0162] The final mixture may be further processed and shaped, for example, by an extrusion operation or by calendering.

[0163] The rubber mixtures according to the invention are particularly suitable for use in vehicle tires, in particular pneumatic vehicle tires. In principle, all tire components, in particular the outer components, particularly preferably Rim Strip In the case of treads having a cap / base construction, the rubber mixture according to the invention is preferably used at least in the cap.

[0164] For use in vehicle tires, the mixture as a finished pre-vulcanization mixture is preferably formed into the corresponding shape of the outer component and applied in known manner during the manufacture of green vehicle tires.

[0165] The production of the rubber mixture according to the invention for use as any other body mixture in vehicle tires is carried out as described above. The difference lies in the shaping after the extrusion / calendering operation of the mixture. The shape of the rubber mixture thus obtained, not yet vulcanized, for one or more different body mixtures is then used to produce green tires.

[0166] Here, the "main body mixture" basically includes a squeegee, an inner liner (inner layer), a core profile, a belt, a shoulder, a belt profile, a carcass, a bead reinforcement, a bead profile, Rim Strip It refers to the rubber mixture for the inner components of the tire, such as the rubber bandages and the like.

[0167] The green tire, which has not yet been cured, is then cured.

[0168] For the use of the rubber mixture of the invention in drive belts and other belts, especially conveyor belts, the extruded, not yet vulcanized mixture is given 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 more plies of the rubber mixture, one and / or more plies of the same and / or different reinforcing elements, and one and / or more further plies of the same and / or other rubber mixtures.

[0169] The present invention further provides a vehicle tire comprising a rubber mixture according to the invention containing a compound according to the invention in at least one of its constituents.

[0170] The vulcanized vehicle tire in at least one component contains a vulcanizate of at least one rubber mixture according to the invention. Those skilled in the art know that most of the substances present, such as rubber, are already present after mixing or may only be present in a chemically modified form after vulcanization.

[0171] In the context of the present invention, "vehicle tires" should be understood to mean pneumatic vehicle tires and solid rubber tires, including industrial tires, as well as tires for construction vehicles, trucks, cars and motorcycles.

[0172] The vehicle tyre according to the invention comprises the rubber mixture according to the invention in at least one external component, the external component preferably being the tread, the sidewall and / or Rim StripIt is preferable if:

[0173] Thus, the vehicle tyre according to the invention may comprise the rubber mixture according to the invention comprising the compound according to the invention of formula I), in particular of formula II), in several components, optionally in a compatible composition. [Example]

[0174] The present invention will now be more specifically clarified with reference to the following examples.

[0175] Compounds of formula II) as preferred embodiments of compounds of formula I) were prepared according to the first synthetic route as follows: Synthesis of 2-(p-phenylenediamine)-methylbenzoate according to scheme XI: [ka]

[0176] The two starting materials are commercially available.

[0177] 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 initially charged 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 (CuI) (0.72 mmol, 0.1 eq), the mixture was stirred at 80 °C overnight. After completion of the reaction, the solvent was distilled off, and the residue was taken up in a mixture of ethyl acetate and 5% by weight aqueous ammonia. Before drying over sodium sulfate, the organic phase was extracted again with 5% ammonia solution, water, and saturated sodium chloride solution. The inorganic salts were separated by filtration, and the solvent was removed under vacuum. 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). 1H-NMR (Nuclear Magnetic Resonance) (500MHz,DMSO-d6)δ=9.00(s,1H),7.83(dd,J=8.6,1.7Hz,1H),7.29(ddd,J=8.6,7.0,1.7 Hz,1H),6.91(d,J=8.5Hz,2H),6.79(dd,J=8.6,1.1Hz,1H),6.67-6.56(m,3H),5.07(s,2H),3.84(s,3H). 13 C-NMR(126MHz,DMSO-d6)δ=168.7,150.4,146.9,134.9,128.4,126.6,116.0,115.1,113.4,110.0,52.2.

[0178] 2-(N) via Scheme XII 1 -(4-methylpentan-2-yl)-N 4 Synthesis of (p-phenylenediamine)-methylbenzoate: [ka]

[0179] 6.80 g (28.1 mmol, 1 eq) of 2-(p-phenylenediamine)-methylbenzoate, 1.18 g of palladium on carbon (Pd / C) (5%) (0.2 g for 4.67 mmol of substrate), and 50.0 mL of methyl isobutyl ketone (MIBK) were weighed into a stainless steel autoclave equipped with a Teflon liner. The reaction mixture was then subjected to hydrogen (H) at a pressure of 20 bar and stirred at 60 °C for 10 h. At the end of the reaction, the excess hydrogen was released, and the suspension was filtered through Celite® and washed with ethanol. The filtrate was evaporated to dryness and dried under vacuum. 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). 1H NMR(500MHz,DMSO-d6)δ=9.01(s,1H),7.83(dd,J=8.1,1.7Hz,1H),7.30(ddd,J=8.7,7.0,1.7Hz ,1H),6.95(d,J=8.7Hz,2H),6.81(dd,J=8.6,1.1Hz,1H),6.66-6.56(m,3H),5.32(d,J=8.6Hz,1 H),3.84(s,3H),3.44(dq,J=8.6,6.7Hz,1H),1.74(dt,J=13.4,6.7Hz,1H),1.46(dt,J=14.0,7. 1Hz,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)δ=168.7,150.4,146.6,134.9,131.6,127.7,126 .8,116.0,113.4,113.3,109.9,52.2,46.4,46.0,25.00,23.2,23.1,21.2. ES-IMS (Electrospray Ionization Mass Spectrometry) [M+H] + =327.

[0180] 2-(N) via Scheme XII 1 -(4-methylpentan-2-yl)-N 4 Synthesis of (p-phenylenediamine)-benzoic acid: [ka]

[0181] 3.90 g of 2-(N)-2H-COOH in 40 mL of degassed dioxane and 50 mL of degassed aqueous sodium hydroxide (NaOH) (2 molar). 1 -(4-methylpentan-2-yl)-N 4(p-phenylenediamine)-methylbenzoate (12.0 mmol, 1 eq) was heated under reflux overnight. Once the reaction had reached room temperature (RT), the pH was adjusted to pH 7 with ice cooling. The mixture was extracted three times with 2-methyltetrahydrofuran (2-MTHF), and the combined organic phases were extracted with water and saturated sodium chloride solution and dried over sodium sulfate. A dark green solid was obtained; yield 3.70 g (99% of theory). 1 H-NMR(500MHz,DMSO-d6)δ=10.91(br s,1H),7.85(dd,J=7.7,1.8Hz,1H),7.04(ddd,J=8.6,7.0,1.8Hz,1H),6.89(d,J=8.7Hz,2H), 6.81(dd,J=8.3,1.1Hz,1H),6.55(d,J=8.7Hz,2H),6.48(ddd,J=8.0,7.1,1.2Hz,1H),5.05(br s,1H),3.41(q,J=6.5Hz,1H),1.74(dt,J=13.5,6.7Hz,1H),1.45(dt,J=13.4,7.1Hz,1H),1.2 1(dt,J=13.5,6.9Hz,1H),1.08(d,J=6.1Hz,3H),0.92(d,J=6.7Hz,3H),0.88(d,J=6.5Hz,3H). 13 C-NMR(126MHz,DMSO)δ=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.

[0182] Synthesis of 2-(1,3-dimethylbutylamino)-acridin-9(10H)-one (compound of formula II) according to scheme XIV: [ka]

[0183] 7.80 g of 2-(N 1 -(4-methylpentan-2-yl)-N 4(p-Phenylenediamine)-benzoic acid (25.0 mmol, 1 eq) was stirred in 40 mL of polyphosphoric acid (PPA) at 130 °C for 16 h. Once the reaction reached 60 °C, PPA was slowly hydrolyzed by adding water. The solution was then cooled to RT, and the pH was adjusted to 7. The mixture was extracted three times with 2-MTHF, and the combined organic phases were extracted with water and saturated sodium chloride solution and dried over sodium sulfate. Inorganic salts were removed by filtration, and the solvent was removed under vacuum. The residue was then purified by column chromatography on silica gel (cyclohexane / EE + 1% triethylamine (TEA) or cyclohexane / tetrahydrofuran (THF) + 1% TEA). A yellow-bronze solid was obtained; yield 5.30 g (72% of theory). 1 H-NMR(500MHz,DMSO-d6)δ=11.47(s,1H),8.19(dd,J=8.2,1.5Hz,1H),7.62(ddd,J=8.4,6.8,1 .6Hz,1H),7.47(d,J=8.4Hz,1H),7.37(d,J=8.8Hz,1H),7.24-7.09(m,3H),5.48(d,J=8.3Hz,1 H),3.51(dq,J=7.8,6.3Hz,1H),1.77(dt,J=13.4,6.7Hz,1H),1.51(dt,J=13.9,7.1Hz,1H),1. 26(dt,J=13.6,6.8Hz,1H),1.14(d,J=6.2Hz,3H),0.95(d,J=6.6Hz,3H),0.89(d,J=6.6Hz,3H). 13 C-NMR(126MHz,DMSO)δ=176.4,143.7,140.5,133.2,132.7,126.4,123.8,12 2.3,120.3,119.8,118.8,117.6,102.9,46.3,46.2,25.0,23.2,23.1,20.9. ESI-MS [M+H] + =295.

[0184] 2-(N 1 -(4-methylpentan-2-yl)-N 4Alternative synthesis of 2-(1,3-dimethylbutylamino)-acridin-9(10H)-one (compound of formula II) from ... [ka]

[0185] 4.70g of 2-(N 1 -(4-methylpentan-2-yl)-N 4 (p-Phenylenediamine)-methylbenzoate (2.14 mmol, 1 eq) was dissolved in 40 mL of sulfuric acid (H2SO4) (13.5 M) and stirred at 115 °C for 16 h. Once the reaction reached RT, the pH was adjusted to pH 7 with ice cooling. The mixture was extracted three times with 2-MTHF, and the combined organic phases were extracted with water and saturated sodium chloride solution and dried over sodium sulfate. The inorganic salts were removed by filtration, and the solvent was removed under vacuum. The residue was then purified by column chromatography on silica gel (cyclohexane / EE + 1% TEA) or cyclohexane / THF + 1% TEA). A yellow-bronze solid was obtained; yield 2.90 g (69% of theory). 1 H-NMR(500MHz,DMSO-d6)δ=11.47(s,1H),8.19(dd,J=8.2,1.5Hz,1H),7.62(ddd,J=8.4,6.8,1 .6Hz,1H),7.47(d,J=8.4Hz,1H),7.37(d,J=8.8Hz,1H),7.24-7.09(m,3H),5.48(d,J=8.3Hz,1 H),3.51(dq,J=7.8,6.3Hz,1H),1.77(dt,J=13.4,6.7Hz,1H),1.51(dt,J=13.9,7.1Hz,1H),1. 26(dt,J=13.6,6.8Hz,1H),1.14(d,J=6.2Hz,3H),0.95(d,J=6.6Hz,3H),0.89(d,J=6.6Hz,3H). 13C-NMR(126MHz,DMSO)δ=176.4,143.7,140.5,133.2,132.7,126.4,123.8,12 2.3,120.3,119.8,118.8,117.6,102.9,46.3,46.2,25.0,23.2,23.1,20.9. ESI-MS [M+H] + =295.

[0186] Following a further synthetic route, compounds of formula II) were synthesized as follows:

[0187] First, 2-nitroacridin-9(10H)-one is reacted with 2-nitroacridin-9(10H)-one according to Scheme YI): [ka] (Here, K2CO3 represents potassium carbonate and DMF represents dimethylformamide.) It was synthesized according to R. Freyer J. Chem. 1963, 4979-5004 as shown in

[0188] This is shown in scheme YII): [ka] was used in the synthesis of 2-(1,3-dimethylbutylamino)-acridin-9(10H)-one (compound of formula II) according to

[0189] 0.55 g (2.62 mmol, 1 eq) of 2-nitroacridin-9(10H)-one, 0.23 g of platinum (5%) (0.4 g for 4.67 mmol of substrate), and 20.0 mL of methyl isobutyl ketone were weighed into a stainless steel autoclave equipped with a Teflon liner. The reaction mixture was then subjected to hydrogen at a pressure of 40 bar and stirred at 140°C for 10 hours. At the end of the reaction, the excess hydrogen was released, and the suspension was filtered through Celite® and washed with ethanol. The filtrate was evaporated to dryness and dried under vacuum. The residue was analyzed by LC-MS. The results are shown in Table 1.

[0190] The material can be purified by column chromatography on silica gel (cyclohexane / ethyl acetate 10:1→1:1). Pale yellow solid.

[0191] [Table 1]

[0192] Measurement of oxidative induction time (OIT) The compound of formula II) was studied under laboratory conditions for its potential protective effect as an ageing stabilizer by measuring the oxidation induction time.

[0193] For this purpose, the compound of formula II) as well as 6-PPD were in each case mixed with a polymer (liquid synthetic polyisoprene (IR), LIR-50, Kuraray, weight average molecular weight distribution M w = 54000 g / 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 20 K / min (Kelvin / min) to 170°C, heating rate 1 K / min to 180°C; purge gas: nitrogen (N2), volume flow rate 50 ml / min).

[0194] The specimen was isothermally maintained at 180°C under N2 atmosphere, and then the atmosphere was switched to O2 atmosphere (volume flow rate 50 ml / min).

[0195] DSC (differential scanning calorimetry) was used to determine the oxidation via peaks.

[0196] The time (min) until oxidation was measured.

[0197] The results compared with the known aging stabilizer 6-PPD are summarized in Table 2.

[0198] [Table 2]

[0199] Taking into account a measurement accuracy of ± (plus / minus) 10 minutes, it is clear that the compound of formula II) actually achieves a significantly better protective effect, since it takes longer for the polymer to be decomposed by oxygen. The compounds of the invention of formula I) / formula II) are therefore more environmentally friendly and less harmful to health than further representatives of the 6-PPD / substance class as mentioned above, and are also better ageing stabilizers.

[0200] For use in rubber mixtures for vehicle tyres, the compounds of the invention of formula I), e.g. formula II), are added in place of the ageing stabilizers known in the prior art, such as, for example, 6PPD, 7PPD or IPPD, in a manner known to those skilled in the art, during one of the mixing stages during the preparation of the rubber mixture.

[0201] Therefore, compounds of formula II) were incorporated into exemplary rubber mixtures according to the invention, as shown in Table 3. The resulting examples of the invention are labeled E1.

[0202] Serving as a comparison is rubber mixture V1, which contains 6PPD instead of the compound of formula II) as ageing stabilizer, the rest of the composition being identical. The amounts in Table 3 are expressed in phr.

[0203] The mixtures were prepared in laboratory mixers with a volume of 300 ml to 3 liters under standard conditions in three stages, according to a process customary in the rubber industry. In the first stage (premixing stage), all components except the vulcanization system (sulfur and vulcanization-affecting substances) were mixed for 200 to 600 seconds at 145 to 165 °C, with a target temperature of 152 to 157 °C. In the second stage, the mixture from the first stage was mixed again. In the third stage (final mixing stage), the vulcanization system was added to obtain the final mixture, which was mixed for 180 to 300 seconds at 90 to 120 °C.

[0204] Test specimens were produced from all mixtures by vulcanization under pressure at 160°C–170°C after t95–t100 (measured using a traveling die rheometer according to ASTM D 5289-12 / ISO 6502).

[0205] Also, some specimens of both V1 and E1 were aged (70°C in air for 28 days).

[0206] For all specimens, the following material properties typical for the rubber industry were determined: Resilience at room temperature (RT) according to ISO 4662 or ASTM D 1054 Elongation at break at room temperature (RT) according to DIN 53 504

[0207] For V1 and E1, the difference between the values ​​of the unaged and aged samples was determined in each case.

[0208] The values ​​obtained for V1 were in each case normalized to 100% for reference.

[0209] The values ​​obtained for E1 (difference between unaged and aged) are reported as % performance against this respective V1 criterion, with values ​​above 100% being favorable.

[0210] As can be seen from Table 3, the compounds of formula II) according to the invention, as representatives of compounds of formula I), provide improved aging stabilization, since important properties such as elongation at break and rebound resilience are in each case at higher levels in E1 than in V1 after aging.

[0211] [Table 3] The present application relates to the invention described in the claims, but may also include the following as other aspects. 1. Formula I): [ka] [In the formula, R 1 teeth, xi) an aromatic group, wherein the aromatic group optionally has 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 4 ~C 12 basis, and xiii) aromatic and aliphatic C 1 ~C 12 Combination with groups wherein the group R 2 and R 3 are, independently of one another, the same or different, linear, branched and cyclic, saturated and unsaturated, aliphatic C groups optionally bearing one or more halogen substituents; 1 ~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, wherein n takes the value 0 or 1 or 2 or 3 or 4, and when n is 2 or 3 or 4, the group R 3 are, independently of one another, identical or different, wherein m takes the value 0 or 1 or 2 or 3, and when m is 2 or 3, the group R 2 are, independently of each other, identical or different] Compound. 2. The compound according to claim 1, wherein n is 0 (zero). 3. The compound according to 1 or 2 above, wherein m is 0 (zero). 4.R 1 is bonded to the nitrogen atom (N) via a tertiary carbon atom. 5.R 1 5. The compound according to any one of the above items 1 to 4, characterized in that is a branched alkyl radical having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms. 6.R 1 is selected from 1,3-dimethylbutyl radicals and cyclohexyl radicals; R 1 6. The compound according to any one of the above items 1 to 5, wherein is preferably a 1,3-dimethylbutyl radical. 7.Formula II):

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Claims

1. Formula I): 【Chemical 1】 [In the formula, R １ teeth, xi) aromatic group, and xii) branched and cycloaliphatic C ４ ~C １２ basis, and xiii) an aromatic group and an aliphatic C １ ~C １２ Combination with groups wherein the group R ２ and R ３ may be the same or different, independently of one another, and may be linear, branched, or cyclic, saturated or unsaturated, aliphatic C １ ~C １２ and aryl groups, wherein n has a value of 0 or 1 or 2 or 3 or 4, and when n is 2 or 3 or 4, the group R ３ are, independently of one another, identical or different, In the formula, m takes the value 0 or 1 or 2 or 3, and when m is 2 or 3, the group R ２ are, independently of each other, identical or different.

1. A rubber mixture containing a compound of formula (I) above, which contains at least one diene rubber.

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

3. 3. A rubber mixture according to claim 1, wherein m is 0 (zero).

4. R １ 3. Rubber mixture according to claim 1 or 2, characterized in that is linked to the nitrogen atom (N) via a tertiary carbon atom.

5. R １ 3. Rubber mixture according to claim 1, characterized in that is a branched alkyl radical having from 4 to 12 carbon atoms.

6. R １ 3. A rubber mixture according to claim 1, wherein is selected from 1,3-dimethylbutyl radicals and cyclohexyl radicals.

7. The compound has formula II: 【Chemistry 2】 3. A rubber mixture according to claim 1 or 2, characterized in that it has the structure

8. 3. The rubber mixture according to claim 1 or 2, which contains at least one diene rubber selected from the group consisting of natural polyisoprene (NR 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.

9. A vehicle tire comprising, at least in one of its components, a rubber mixture according to claim 1 or 2.

10. A vehicle tire comprising a rubber mixture according to claim 1 or 2 in at least one outer component, said outer component being the tread, the sidewall and / or the rim strip.

11. Use of a compound as defined in claim 1 or 2 as an ageing stabilizer in vehicle tires.

12. The following process steps: a) Formulas A) and B) 【Chemistry 3】 providing a compound of formula (I); b) reacting said compounds A) and B) with each other in the presence of a base and a catalyst to form a compound of formula C): 【Chemistry 4】 wherein the base is selected from the group consisting of potassium carbonate, potassium phosphate, sodium carbonate, sodium phosphate, cesium carbonate, sodium tert-butoxide, and potassium tert-butoxide, and the catalyst is a catalyst that catalyzes via copper coupling; c) reacting said compound of formula C) with hydrogen or a hydrogenation reagent and a ketone or aldehyde to form a compound of formula D): 【Chemistry 5】 obtaining a compound of formula (I); d) optionally reacting said compound of formula D) to form a compound of formula E): 【Chemistry 6】 obtaining a compound of formula (I); e) reacting said compound of formula D) or E) with an acid to obtain a compound of formula I): 【Chemistry 7】 The process of obtaining A method for preparing a compound of formula I comprising: In the formula, R １ teeth, xi) aromatic group, and xii) branched and cycloaliphatic C ４ ~C １２ basis, and xiii) an aromatic group and an aliphatic C １ ~C １２ Combination with groups wherein the group R ２ and R ３ may be the same or different, independently of one another, and may be linear, branched, or cyclic, saturated or unsaturated, aliphatic C １ ~C １２ and aryl groups, wherein n has a value of 0 or 1 or 2 or 3 or 4, and when n is 2 or 3 or 4, the group R ３ are, independently of one another, identical or different, In the formula, m takes the value 0 or 1 or 2 or 3, and when m is 2 or 3, the group R ２ are, independently of one another, identical or different; method.

13. 13. The process according to claim 12, characterized in that the reaction in step c) with hydrogen and the aldehyde or ketone is carried out using a hydrogenation catalyst and at a temperature of 120°C to 150°C, the reaction mixture is subjected to hydrogen at a pressure of 35 to 45 bar, and the reaction is carried out in an autoclave or in a separate pressure reactor.

14. Formula I): 【Chemistry 8】 [In the formula, R １ is a branched alkyl radical having 4 to 12 carbon atoms, In the formula, the group R ２ and R ３ are, independently of one another, the same or different, linear, branched and cyclic, saturated and unsaturated, aliphatic C groups optionally bearing one or more halogen substituents; １ ~C １２ groups, aryl groups optionally bearing one or more halogen substituents, and halogen groups, cyano groups, ester groups, ketone groups, ether groups, and thioether groups, wherein n takes the value 0; In the formula, m takes the value 0. Compound.

15. Formula II): 【Chemistry 9】 15. The compound of claim 14, characterized in that it has the structure:

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