Compounds, rubber blends containing said compounds, vehicle tires containing said rubber blend in at least one component, processes for producing said compounds, and use of said compounds as anti-aging agents and / or anti-ozone agents and / or dyes

Abstract

The present invention relates to a compound, a rubber mixture containing the compound, a vehicle tyre comprising at least one constituent of the rubber mixture, a process for the preparation of the compound and the use of the compound as ageing protection agent and / or antiozonant and / or dye. 1 benzyl group, 1-phenylalkyl group having a total of 7 to 18 carbon atoms, and linear, branched and cyclic aliphatic C3 to C 12 The compound is selected from the group consisting of the groups. TIFF2024529396000027.tif30170

Description

Technical Field

[0001] The present invention relates to a compound, a rubber mixture containing the compound, a vehicle tire including the rubber mixture in at least one component, a manufacturing process thereof, and the use of the compound as an anti-aging agent and / or an anti-ozone agent and / or a dye.

Background Art

[0002] It is known that vehicle tires and technical rubber articles employ high molecular materials such as rubber in particular.

[0003] In the case of long-term storage, and particularly in end-uses that are often hot, natural rubber and synthetic polymers (such as IR, BR, SSBR, ESBR, etc.), as well as natural and synthetic oils, fats and lubricants, are subject to oxidation reactions that adversely affect their original desired properties. Depending on the type of polymer, the polymer chains become shorter until the material liquefies or subsequent hardening of the material occurs.

[0004] Therefore, anti-aging agents play a decisive role in the durability of vehicle tires and other technical rubber articles.

[0005] Known anti-aging agents 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 reactive with oxygen or ozone, or free radicals formed such as alkyl, alkoxy and alkylperoxy radicals, thereby scavenging them and thus protecting rubber etc. from further oxidation reactions.

[0007] However, the drawback of this class of substances is that they are suspected of being carcinogenic.

[0008] An anti-aging stabilizer that reacts particularly with ozone to achieve its scavenging is also called an "ozone decomposer".

SUMMARY OF THE INVENTION

PROBLEM TO BE SOLVED BY THE INVENTION

[0009] The object of the present invention is to provide a novel compound that can be used as an anti-aging stabilizer for vehicle tires or other industrial rubber articles, in particular, which has a lower potential hazard in combination with sufficient solubility in each matrix, for example, particularly in polymers. This is intended to continue to provide optimal protection from oxygen and ozone, reduce harm to health, and prevent the tendency of blooming.

MEANS FOR SOLVING THE PROBLEM

[0010] This object is achieved by the compound of the present invention as claimed in claim 1, by the rubber mixture of the present invention containing this compound, and also by the vehicle tire of the present invention containing the rubber mixture of the present invention in at least one component. This object is further achieved by using this compound as an anti-aging stabilizer and / or an anti-ozone degradation agent.

[0011] The compound according to claim 1 can further be used as a dye.

[0012] This object is further achieved by the process according to the present invention for producing the compound according to the present invention.

[0013] The compound as claimed in claim 1 has the general formula I):

CHEMICAL

[0014] When n is 0 (zero) or 1 or 2 or 3, it is obvious to those skilled in the art that each further hydrogen atom is bonded to the corresponding carbon atom of the saturated ring instead of R 3 . Similarly, when m is 0 or 1 or 2, all remaining free positions in the benzene ring of the structure are hydrogen atoms.

[0015] For each (benzene) ring of the structure, (R 2 ) m and (R 3 ) n as well as the expression of the bond of R 1 HN should be understood by those skilled in the art to mean that these groups can be arranged at any position on each (benzene) ring, except that in the case of the benzene ring, more than two will not be at the same position at the same time in any case, as would already be excluded in the case of the benzene ring by the tetravalence of the carbon atoms.

[0016] In the context of the present invention, the type "C3-C 12The description of "radical" should be understood to mean a radical having 3 to 12 carbon atoms. Independently thereof, "C1" is used to describe the position of the most highly oxidized carbon atom / highest priority carbon atom according to the Cahn-Ingold-Prelog rules (CIP). What is meant in each context will be clear to the person skilled in the art.

[0017] The compounds according to the invention are tetrahydroacridine derivatives. For example, while carbazole is classified as carcinogenic, on the other hand, tetrahydrocarbazole is not classified as carcinogenic. Thus, it is expected by analogy that they exhibit a lower risk potential compared to known anti-aging stabilizers based on aniline (a possible cleavage product of 6-PPD). Since the rubber raw materials can be released by abrasion or other degradation processes, the lower risk potential is an extremely important advantage, especially in technical applications such as in vehicle tires or other rubber products.

[0018] Moreover, the compounds according to the invention have an improved protective effect against oxidation and thus aging, especially of polymers, compared to 6-PPD.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention includes all advantageous embodiments, which are reflected in particular in the claims. The present invention also includes embodiments resulting from combinations of different features having different priorities for these features, such that in particular combinations of a first feature described as "preferred" or in the context of an advantageous embodiment of the invention, with further features described, for example, as "particularly preferred".

[0020] Preferably, n is 0 (zero).

[0021] Preferably, m is 0 (zero).

[0022] R 1It is preferably bonded to a nitrogen atom (N) via a tertiary carbon atom. Therefore, the C1 atom is preferably a tertiary carbon atom.

[0023] In the context of the present invention, the term "tertiary carbon atom" should be understood to mean a carbon atom bonded to only one hydrogen atom.

[0024] R 1 is particularly preferably a branched alkyl group having 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms in sequence, or a 1-phenylethyl group having a total of 7 to 10 carbon atoms. At least one branch is present on the C1 carbon, i.e., on the carbon atom bonded to the nitrogen atom (N), and thus it is preferable to make the C1 atom a tertiary carbon atom.

[0025] R 1 is very particularly preferably selected from 1,3-dimethylbutyl, 1-phenylethyl and cyclohexyl groups; R 1 is very particularly preferably a 1,3-dimethylbutyl group in sequence.

[0026] In a preferred embodiment, the compound has the formula II):

Chemical formula

[0027] The compound of formula II) makes it possible to achieve a further further improvement in protection against oxidation and thus aging, especially in polymers. At the same time, the compound of formula II) is less harmful to health than, for example, 6-PPD or other representatives of this class of substances as described above.

[0028] Therefore, compared with 6-PPD, the compound of formula III) is a better, less harmful to health and environmentally friendly anti-aging stabilizer.

[0029] Compounds of formula (I) and formula (II) and all of the present invention described above are particularly suitable as anti-aging stabilizers and / or anti-ozonants in, inter alia, 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 vehicle tires and / or technical rubber articles such as oils and / or lubricants.

[0030] Accordingly, the present invention further provides for the use of a compound according to the invention as an anti-aging stabilizer and / or anti-ozonant in, inter alia, 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 vehicle tires and / or industrial rubber articles such as oils and / or lubricants.

[0031] For the use of the compounds of formula (I) and formula (II) and all of the foregoing in the listed articles or substances, the compounds are used in a composition and are incorporated into and used in the composition.

[0032] In vehicle tires or other industrial rubber articles, the composition is in particular in a rubber mixture.

[0033] The present invention further provides for the use of compounds of formula (I) and formula (II) and all of the present invention as described above as dyes in fibers and / or polymers and / or papers and / or (decorative) paints and coatings.

[0034] A further aspect of the present invention is the following process steps: a1) formula A1)

Chemical formula

Chem.

Chem.

[0035] 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).

[0036] The reaction according to step b1) is preferably carried out in a polar solvent, particularly dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). Dimethylformamide (DMF) is particularly preferred.

[0037] Further preferred process features are listed together with the preferred process features of a further process for producing a compound of formula I).

[0038] The present invention further provides at least the following process steps: a2) A compound of formula A2):

Chem.

Chem.

[0039] The halogenating agent in step c2) is particularly an acidic halogenating agent. The halogenating agent in step c2) is preferably selected from the group consisting of PCl3, POCl3, PBr3 and SOCl2. It is very particularly preferred to use PCl3 or POCl3.

[0040] The compound of formula C2) is preferably transferred to a pressure vessel after isolation, preferably in sequence without further purification. The reaction according to step d2) for obtaining the compound of formula D2) is preferably carried out in a pressure vessel, i.e., in a vessel suitable for relatively high pressures, such as an autoclave or another pressure reactor, inter alia.

[0041] The reaction by step d2) is preferably carried out at a temperature of 200 °C to 240 °C, particularly and for example 220 °C.

[0042] The acid in step d2) is particularly a water-soluble acid such as acetic acid, and particularly a diluted aqueous solution such as acetic acid diluted with water is particularly used. The acid is particularly also a non-nucleophilic acid.

[0043] "Hydriding reagent" should be understood to mean a compound that brings about hydrogenation. Such reagents include hydrides, particularly metal hydrides, as known to those skilled in the art.

[0044] Suitable hydrides include, for example, sodium borohydride.

[0045] In the context of the present invention, hydrogen is not additionally listed under "hydriding reagent" since it is explicitly mentioned as an alternative. Nevertheless, the term "hydriding reagent" will be understood to encompass all reagents that form hydrogen which effects hydrogenation in situ.

[0046] The reactions in steps c1) and e2) with hydrogen (H2) and a ketone or aldehyde (R 1 =O), preferably a ketone, are preferably carried out using a hydrogenation catalyst.

[0047] The reaction by step c1) is preferably carried out at a temperature of 120 °C to 150 °C, particularly and for example 140 °C.

[0048] In step c1), the reaction mixture is preferably subjected to hydrogen at a pressure of 35 to 45 bar, particularly and for example 40 bar, and is preferably then stirred for 1 to 20 hours, preferably 8 to 13 hours, particularly and for example 10 hours. The reaction by step e2) is preferably carried out at a temperature of 50 °C to 70 °C, particularly and for example 60 °C.

[0049] In step e2), the reaction mixture is preferably subjected to hydrogen at a pressure of 15 to 25 bar, in particular for example 20 bar, and is subsequently preferably stirred for 1 to 20 hours, preferably 8 to 13 hours, in particular for example 10 hours.

[0050] The ketones in steps c1) and e2) are ketone derivatives of the following radical R 1 and in the case of aldehydes, are thus aldehyde derivatives.

[0051] For the sake of simplicity, since radical R 1 is the moiety remaining on the nitrogen atom after reaction with an aldehyde or ketone, the simplified formula R 1 =O is used for the aldehyde or ketone.

[0052] It is preferred to use the ketone methyl isobutyl ketone.

[0053] The reaction with hydrogen in steps c1) and e2) is preferably carried out in a vessel suitable for relatively high pressures, in particular an autoclave or another pressure reactor.

[0054] The reaction with hydrogen is preferably a process step carried out using a suitable catalyst referred to as a "hydrogenation catalyst" in the context of the present invention.

[0055] It is preferred that the hydrogenation catalyst is a noble metal catalyst, in particular for example palladium (Pd) or platinum (Pt). It is preferred that the noble metal is used on carbon (C) such as palladium on carbon (Pd / C).

[0056] Furthermore, it is also possible to use other known catalysts such as Raney nickel or copper chromite.

[0057] In processes c1) and e2), the solvent can be either a ketone or an aldehyde, especially a ketone, if it is in liquid form, or an inert solvent such as toluene or xylene 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.

[0058] It is preferred to use a ketone or an aldehyde, particularly preferably a ketone, in liquid form as the solvent. This makes it possible to avoid additional substances such as toluene or xylene.

[0059] In particular, by process c), the reaction product is a substance mixture containing the compound of formula I), where preferably purification, for example on silica gel, for example column chromatography, follows in process c1) / e2).

[0060] As described above, the present invention further provides a rubber mixture.

[0061] The rubber mixture according to the present invention contains a compound of formula I), in particular of formula II). The rubber mixture according to the present invention can in principle be any rubber mixture in which the novel compounds of the present invention, in particular of formula I), in particular of formula II), are low-toxic and act as anti-aging agents and / or anti-ozone agents.

[0062] The rubber mixture of the present invention contains at least one rubber.

[0063] Preferably, the rubber mixture according to the present invention contains 0.1 to 10 phr, particularly preferably 0.1 to 7 phr, very particularly preferably 1 to 6 phr of the compound of formula I), in particular of formula II).

[0064] The unit "phr" (parts per 100 parts by weight of rubber) used in this written description is a conventional indication of the amount in mixture formulations in the rubber industry. The dosage in parts by weight of the individual substances is, in this document, based on 100 parts by weight of the total mass of all high-molecular-weight (M w exceeding 20,000 g / mol) rubbers present in the mixture.

[0065] In an advantageous embodiment of the present invention, the rubber mixture according to the present invention contains at least one diene rubber.

[0066] Accordingly, the rubber mixture may contain a diene rubber or a mixture of two or more different diene rubbers.

[0067] A diene rubber is a rubber formed by polymerizing or copolymerizing a diene and / or a cycloalkene, and for this purpose, has a C═C double bond either in the main chain or in a side group.

[0068] 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, a liquid rubber having a molecular weight M w exceeding 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, and is selected from the group consisting of.

[0069] Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber and / or ethylene-propylene-diene rubber are particularly used in the manufacture of industrial rubber articles such as belts, drive belts and hoses and / or shoe soles. It is preferable to employ a mixing composition known to those skilled in the art for these rubbers, which is specific from the viewpoints of fillers, plasticizers, vulcanization systems and additives.

[0070] The natural and / or synthetic polyisoprenes of all embodiments can 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 is available by stereospecific polymerization in solution with a Ziegler-Natta catalyst or using a fine lithium alkyl. 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.

[0071] Mixtures of one or more natural polyisoprenes and one or more synthetic polyisoprenes are further contemplated.

[0072] In the context of the present invention, the term "natural rubber" should be understood to mean natural rubber obtainable from Hevea rubber trees and from "non-Hevea" sources. Non-Hevea sources include, for example, guayule shrubs and dandelions such as TKS (Russian dandelion; Taraxacum kok-saghyz).

[0073] When the rubber mixture of the present invention contains butadiene rubber (i.e., BR, polybutadiene), this can be of any type known to those skilled in the art. These include what are called high-cis and low-cis types, where polybutadiene having a cis content of 90% by weight or more is referred to as the high-cis type and polybutadiene having a cis content of less than 90% by weight is referred to as the low-cis type. An example of low-cis polybutadiene is Li-BR (lithium catalyst butadiene rubber) having a cis content of 20% to 50% by weight. In high-cis BR, particularly good properties and low hysteresis are achieved in the rubber mixture.

[0074] The polybutadiene employed may be end-group modified by modification and functionalization, and / or may be functionalized along the polymer chain. The modification may be selected from modification with a hydroxyl group and / or an ethoxy group and / or an epoxy group and / or a siloxane group and / or an amino group and / or an aminosiloxane and / or a carboxyl group and / or a phthalocyanine group and / or a silane-sulfide group. However, further modifications known to those skilled in the art, also referred to as functionalizations, are also useful. A metal atom may be a constituent of such a functionalization.

[0075] If at least one styrene-butadiene rubber (styrene-butadiene copolymer) is present in the rubber mixture, this 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.

[0076] The styrene-butadiene copolymer used may be end-group modified and / or functionalized along the polymer chain by the modifications and functionalizations mentioned above for polybutadiene.

[0077] 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.

[0078] In a particularly preferred embodiment of the present invention, 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).

[0079] In a particularly advantageous embodiment of the present invention, the rubber mixture contains at least one natural polyisoprene (NR) and / or synthetic polyisoprene (IR), preferably in an amount of 50 to 100 phr. In a particularly advantageous embodiment of the present invention, it contains in an amount of 80 to 100 phr, very particularly preferably 95 to 100 phr, and then preferably 100 phr. Such a rubber mixture exhibits optimized tear and wear characteristics, particularly in combination with good processability and recovery stability.

[0080] If the rubber mixture contains less than 100 phr of NR and / or IR, the rubber mixture preferably contains, as a 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).

[0081] In a further particular advantageous embodiment of the present invention, the rubber mixture contains at least one natural polyisoprene (NR), preferably in an amount of 5 to 55 phr, and in a particular advantageous embodiment of the present invention, in an amount of 5 to 25 phr, very particularly preferably 5 to 20 phr. Such a rubber mixture exhibits particularly good processability, vulcanization return stability, optimized tear properties, and optimal rolling resistance characteristics.

[0082] In a further particular advantageous embodiment of the present invention, the rubber mixture contains 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 particular advantageous embodiment of the present invention, in an amount of 15 to 40 phr. Thereby, particularly good tear and wear characteristics of the rubber mixture according to the present invention, as well as optimal braking characteristics, are achieved.

[0083] In a further specific 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 in an amount of 30 to 80 phr, and in a particular advantageous embodiment of the present invention, in an amount of 50 to 70 phr. Thereby, particularly good rolling resistance characteristics of the rubber mixture according to the present invention are achieved. 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 well-balanced property profile.

[0084] Preferably, the rubber mixture contains at least one filler in an amount of 30 to 500 phr, particularly preferably in an amount of 50 to 400 phr, and then preferably in an amount of 80 to 300 phr.

[0085] In an advantageous embodiment of the present invention, the filler is preferably a reinforcing filler selected from the group consisting of carbon black and silicon dioxide.

[0086] Suitable carbon blacks include any carbon black type known to those skilled in the art. Preferably, the carbon black is selected from industrial carbon black and pyrolytic carbon black, and more preferably industrial carbon black.

[0087] The carbon black has an iodine value according to ASTM D1510, which is also known as the iodine adsorption amount 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 according to ASTM D2414 of 30 to 200 ml / 100 g, preferably 70 to 200 ml / 100 g, particularly preferably 90 to 200 ml / 100 g.

[0088] The DBP value according to ASTM D2414 determines the specific absorption volume of the carbon black or light-colored filler with respect to dibutyl phthalate.

[0089] In particular, the use of such types of carbon black in rubber mixtures for vehicle tires ensures an optimal compromise between wear resistance and heat storage, which in turn affects the ecologically relevant rolling resistance.

[0090] 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, for example, in particular carbon black of type N 339.

[0091] Silicon dioxide is preferably amorphous silicon dioxide, for example, precipitated silica also known as precipitated silica. However, it is also alternatively possible to use, for example, pyrogenic silicon dioxide.

[0092] However, it is particularly preferred to use finely divided precipitated silica having a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) of 35 to 400 m2 / g, preferably 35 to 350 m2 / g, more preferably 85 to 320 m2 / g, most preferably 120 to 235 m2 / g and a CTAB surface area (according to ASTM D 3765) of 30 to 400 m2 / g, preferably 30 to 330 m2 / g, more preferably 80 to 300 m2 / g, most preferably 115 to 200 m2 / g. Such silica provides particularly good physical properties of the vulcanized rubber, for example, in rubber mixtures for tire treads. Advantages in the processing of the mixture due to shortening of the mixing time can also be achieved while maintaining the same product properties, resulting in improved productivity. The silica used can therefore be, for example, the Ultrasil® VN3 type (trade name) manufactured by Evonik, or highly dispersed silica known as HD silica (for example, Zeosil® 1165MP manufactured by Solvay).

[0093] In a particularly advantageous embodiment of the present invention, the rubber mixture contains, as a filler, at least one silica, preferably in an amount of 30 to 500 phr, particularly preferably 50 to 400 phr, and then preferably in an amount of 80 to 300 phr.

[0094] In these amounts, the silica is present in particular alone or as the main filler (more than 50% by weight based on the total amount of the filler).

[0095] In a further advantageous embodiment of the present invention, the rubber mixture contains at least one silica as a further filler, preferably in an amount of 5 to 100 phr, particularly preferably 5 to 80 phr, and then preferably in an amount of 10 to 60 phr.

[0096] In these amounts, the silica is present in particular as a further filler in addition to other main fillers such as carbon black.

[0097] The terms "silicic acid" and "silica" are used synonymously in the context of the present invention.

[0098] In a particularly advantageous embodiment of the present invention, the rubber mixture according to the present invention contains at least one carbon black in an amount of 0.1 to 60 phr, preferably 3 to 40 phr, particularly preferably 5 to 30 phr, and very particularly preferably 5 to 15 phr. In these amounts, the carbon black is present in particular as a further filler in addition to the main filler such as silica.

[0099] In a further advantageous embodiment of the present invention, the rubber mixture according to the present invention contains at least one carbon black in an amount of 30 to 300 phr, preferably 30 to 200 phr, particularly preferably 40 to 100 phr. In these amounts, the carbon black is present alone or as the main filler, and thus, optionally, in combination with silica in the amounts on the lower limit side described above.

[0100] In certain advantageous embodiments of the present invention, the rubber mixture contains at least one carbon black in an amount of 5 to 60 phr, particularly preferably 5 to 40 phr, and at least one silica in an amount of 50 to 300 phr, preferably 80 to 200 phr.

[0101] The rubber mixture may further contain a reinforcing or non-reinforcing additional filler.

[0102] In the context of the present invention, additional (non-reinforcing) fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide, or rubber gels and fibers (such as aramid fibers, glass fibers, carbon fibers, cellulose fibers).

[0103] Furthermore, optionally reinforcing fillers are, for example, carbon nanotubes (discrete CNTs, hollow carbon fibers (HCF) and modified CNTs such as those containing one or more functional groups such as hydroxy, carboxy and carbonyl groups, etc. (CNTs)), graphite and graphene and those known as "carbon-silica two-phase fillers".

[0104] In connection with the present invention, zinc oxide is not contained in the filler.

[0105] The rubber mixture can further contain customary additives in customary parts by weight, which are preferably added in at least one primary mixing stage during the production of the mixture. These additives include: a) Aging stabilizers known from the prior 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'-ditoly-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)thiosulfuric acid and / or its metal salts (for binding carbon black) and silane coupling agents (for binding silica), d) Antiozonant waxes, e) Resins, especially tackifying resins, f) Kneading aids such as 2,2'-dibenzamidodiphenyldisulfide (DBD), and g) Processing aids especially fatty acid esters and metal soaps such as zinc soap and / or calcium soap, h) Plasticizers such as especially aromatic, naphthenic or paraffinic mineral oil plasticizers, such as MES (mild extraction solventate) preferably having a content of polycyclic aromatic compounds of less than 3% by weight according to method IP 346, or RAE (residual aromatic extract), or TDAE (treated distillate aromatic extract) or rubber to liquid (RTL) oil or biomass to liquid (BTL) oil, or triglycerides such as rapeseed oil or factice or hydrocarbon resins or liquid polymers having an average molecular weight (measured by GPC = gel permeation chromatography in accordance with BS ISO 11344:2004) of 500 to 20,000 g / mol.

[0106] When using mineral oil, this is preferably selected from the group consisting of DAE (distillate aromatic extract), RAE (residual aromatic extract), TDAE (treated distillate aromatic extract), MES (mild extract solvate), and naphthenic oil.

[0107] In a particularly advantageous embodiment, the rubber mixture according to the invention, in addition to the compounds of the invention of formula I), in particular formula II), does not contain an anti-aging stabilizer from the group of p-phenylenediamines, in particular those listed above in a). In a particularly preferred embodiment, the rubber mixture according to the invention contains, in particular, 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'-ditoly-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD), preferably selected from the group consisting of these, and contains 0 to 0.1 phr, in particular 0 phr, of a further anti-aging stabilizer based on p-phenylenediamine.

[0108] The p-phenylenediamine, preferably in a very small amount of 0 to 0.1 phr, particularly preferably 0 phr, and the compounds of formula I), in particular formula II), present according to the invention make it possible to achieve an improved protective effect with lower toxicity. The compounds of the invention of formula I), in particular formula II), replace the listed p-phenylenediamines known in the prior art.

[0109] In a further advantageous embodiment of the invention, since at least one further representative of the listed p-phenylenediamine anti-aging stabilizers is present, the compounds according to the invention only partially replace the p-phenylenediamines known in the prior art. This also achieves the advantages according to the invention, although not to the optimum extent.

[0110] In an advantageous embodiment, a dihydroquinoline-based anti-aging agent such as TMQ is present in the rubber mixture in addition to the compound of formula I) according to the invention. In particular, the amount of dihydroquinoline present, such as TMQ, is preferably from 0.1 to 3, in particular from 0.5 to 1.5 phr.

[0111] The antiozonant wax (group d) above is considered separately and, in a preferred embodiment of the invention, is present in the rubber mixture regardless of whether an additional anti-aging agent a) is present.

[0112] The silane coupling agent is of any type known to the person skilled in the art.

[0113] Furthermore, one or more different silane coupling agents can be used in combination with each other. For this reason, the rubber mixture can contain a mixture of different silanes.

[0114] The silane coupling agent reacts with the surface silanol groups or other polar groups of silicon dioxide, in particular silica, either before the addition of the filler to the rubber or during the mixing of the rubber / rubber mixture (in situ) or in the context of a pretreatment (pre-modification).

[0115] Coupling agents known from the prior art are bifunctional organosilanes having at least one alkoxy, cycloalkoxy or phenoxy group as a leaving group on the silicon atom and possibly, after cleavage, having another functional group capable of proceeding to a chemical reaction with the double bonds of the polymer. The groups in the latter can include, for example, the following chemical groups: -SCN, -SH, -NH2 or -S x -(where x = 2 to 8).

[0116] Possible silane coupling agents include, for example, 3-mercaptopropyltriethoxysilane having 2 to 8 sulfur atoms, 3-thiocyanatopropyltrimethoxysilane, or 3,3'-bis(triethoxysilylpropyl) polysulfide, such as 3,3'-bis(triethoxysilylpropyl) tetrasulfide (TESPT), the corresponding disulfide (TESPD), or other mixtures of sulfides with various sulfides having different contents and having 1 to 8 sulfur atoms. TESPT can also be added, for example, as a mixture with carbon black (trade name X50S (registered trademark), manufactured by Evonik).

[0117] For example, blocked mercaptosilanes as known from WO 99 / 09036 can also be used as silane coupling agents. It is also possible to use the silanes described in WO 2008 / 083241 A1, WO 2008 / 083242 A1, WO 2008 / 083243 A1, and WO 2008 / 083244 A1. The silanes that can be used include, for example, those sold by Momentive in the United States under the name NXT in numerous variants, such as 3-octanoylthio-1-propyltriethoxysilane in particular, or those sold by Evonik Industries under the name VP Si 363 (registered trademark).

[0118] The total proportion of further additives is preferably 3 to 150 phr, more preferably 3 to 100 phr, and most preferably 5 to 80 phr.

[0119] Zinc oxide (ZnO) can be included in the overall proportion of further additives in the amounts described above.

[0120] This can be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder. Conventionally used zinc oxide usually has a BET specific surface area of less than 10 m2 / g. However, it is also possible to use zinc oxide having a BET surface area of 10 to 100 m2 / g, such as so-called "nanometer zinc oxide".

[0121] The rubber mixture of the present invention is preferably in a vulcanized form and is particularly used for vehicle tires or other vulcanized industrial rubber articles.

[0122] The terms "vulcanization" and "crosslinking" are used synonymously in the context of the present invention.

[0123] The vulcanization of the rubber mixture of the present invention is preferably carried out in the presence of sulfur and / or a sulfur donor, with the assistance of a vulcanization accelerator, and some vulcanization accelerators can act as sulfur donors simultaneously. The vulcanization accelerator is 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, xanthate vulcanization accelerators, and guanidine vulcanization accelerators.

[0124] It is preferable to use a sulfenamide accelerator selected from guanidine accelerators such as N-cyclohexyl-2-benzothiazolyl sulfenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazyl-2-sulfen morpholide (MBS), N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), and diphenylguanidine (DPG).

[0125] The sulfur donor substance used can be any sulfur donor substance known to those skilled in the art.

[0126] A vulcanization retarder may be present in the rubber mixture.

[0127] In other cases, the production of the rubber mixture according to the invention is carried out by a process customary in the rubber industry, which preferably involves first producing a primary mixture containing all components except the vulcanization system (e.g., sulfur and vulcanization modifiers) in one or more mixing stages. The final mixture is produced by adding the vulcanization system in the final mixing stage.

[0128] The final mixture is, for example, further processed and shaped into a suitable form by an extrusion operation or calendering.

[0129] The rubber mixture according to the invention is particularly suitable for use in vehicle tires, especially pneumatic vehicle tires. In principle, use in all tire components, especially outer components, particularly preferably in the flange profile, tread and / or sidewall, is conceivable. In the case of a tread having a cap / base structure, the rubber mixture according to the invention is preferably used at least within the cap.

[0130] For use in vehicle tires, the mixture as the finished mixture before vulcanization is preferably shaped into the corresponding shape of the outer component and applied in a manner known during the production of green vehicle tires.

[0131] 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. There are differences in the shaping after the extrusion operation / calendering of the mixture. The shape of the as-yet-unvulcanized rubber mixture for one or more different body mixtures thus obtained is then used for the production of green tires.

[0132] Here, the "body mixture" basically refers to a rubber mixture for the inner components of a tire such as a skid, inner liner (inner layer), core profile, belt, shoulder, belt profile, carcass, bead reinforcement, bead profile, flange profile and bandage.

[0133] The as-yet-unvulcanized green tire is then vulcanized.

[0134] For the use of the rubber mixture according to the invention in drive belts and other belts, in particular conveyor belts, the extruded, still unvulcanized mixture is given the appropriate shape and often, simultaneously or subsequently, reinforcing members, such as synthetic fibres or steel cords, are provided. This usually results in a multi-ply structure consisting of one and / or more plies of the rubber mixture, one and / or more plies of equal and / or different reinforcing members, and one and / or more further plies of the same and / or other rubber mixtures.

[0135] The invention further provides a vehicle tyre comprising a rubber mixture according to the invention containing a compound according to the invention in at least one component.

[0136] The vulcanized vehicle tyre in at least one component contains the vulcanizate of at least one rubber mixture according to the invention. It is known to the person skilled in the art that most substances present, such as rubber, can already be present after mixing or only in a chemically modified form after vulcanization.

[0137] In the context of the present invention, "vehicle tyre" is to be understood as meaning pneumatic vehicle tyres and solid rubber tyres, including industrial tyres and tyres for construction site vehicles, trucks, cars and two-wheeled vehicles.

[0138] The vehicle tyre according to the invention preferably contains the rubber mixture according to the invention in at least one external component, where the external component is preferably the tread, the sidewall and / or the flange profile.

[0139] Thus, the vehicle tyre according to the invention may contain the rubber mixture according to the invention, which contains a compound according to the invention of formula I), in particular of formula II), in a plurality of components, optionally in an adapted composition.

Examples

[0140] Hereinafter, the present invention will be made more specifically clear with reference to examples.

[0141] The compound of formula II) as a preferred embodiment of the compound of formula I) was prepared according to the following first synthetic route:

[0142] First, 2-nitroacridine-9(10H)-one was synthesized according to R. Freyer J. Chem. 1963, 4979 - 5004 as shown in Scheme YI):

Chemical formula

[0143] This was used for the synthesis of 7-((4-methylpentan-2-yl)amino)-1,3,4,10-tetrahydroacridine-9(10H)-one (the compound of formula II) according to Scheme YII):

Chemical formula

[0144] 0.55 g (2.62 mmol, 1 eq) of 2-nitroacridine-9(10H)-one, 0.224 g of platinum on carbon (5%) (0.4 g with respect to 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, 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.

[0145]

Table 1

[0146] The substance can be purified on silica gel by column chromatography (cyclohexane / ethyl acetate 10:1→1:1). Pale yellow solid; yield 0.34 g (40% of theory).

[0147] Analysis of 7-((4-methylpentan-2-yl)amino)-1,3,4,10-tetrahydroacridin-9(10H)-one: 1 1H-NMR (nuclear magnetic resonance) (500 MHz, DMSO-d6) δ = 11.02 (s, 1H), 7.23 (d, J = 8.9 Hz, 1H), 7.04 (d, J = 2.7 Hz, 1H), 6.97 (dd, J = 8.9, 2.7 Hz, 1H), 5.35 (d, J = 8.4 Hz, 1H), 3.54 - 3.41 (m, 1H), 2.65 (t, J = 6.2 Hz, 2H), 2.42 (t, J = 6.2 Hz, 2H), 1.85 - 1.60 (m, 5H), 1.48 (dt, J = 13.9, 7.1 Hz, 1H), 1.24 (ddd, J = 13.6, 8.6, 5.8 Hz, 1H), 1.10 (d, J = 6.2 Hz, 3H), 0.93 (d, J = 6.6 Hz, 3H), 0.87 (d, J = 6.6 Hz, 3H). 13 13C-NMR (126 MHz, DMSO) δ = 175.7, 145.0, 144.3, 131.6, 125.2, 121.0, 118.7, 114.0, 102.3, 46.2, 46.2, 27.5, 26.8, 25.0, 23.2, 23.0, 22.7, 22.4, 22.2, 20.9. ESI-MS (electrospray ionization mass spectrometry) [M + H] + = 299.

[0148] Furthermore, the compound of formula II) was synthesized by further synthetic routes as shown in Schemes XI) and XII):

Chemical formula

[0149] The synthesis step according to Scheme XI) was carried out according to the literature s. Cross, R. Matthew et al.; Journal of Medicinal Chemistry (2011), 54(13), 4399 - 4426.

[0150] The synthesis step according to Scheme XII) (7 - ((4 - methylpentan - 2 - yl)amino)-1,3,4,10 - tetrahydroacridin - 9(10H)-one, the molecule of formula II) was carried out as follows: 0.24 g (0.98 mmol, 1 eq) of 6 - nitro - 1,3,4,10 - tetrahydroacridin - 9(2H)-one, 0.082 g of platinum on carbon) (0.4 g with respect to 4.67 mmol of the substrate) and 20.0 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 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, the suspension was filtered through Celite® and washed with ethanol. The filtrate was evaporated to dryness and dried under vacuum; yield 98%; see the above analysis.

[0151] Measurement of Oxidation Induction Time (OIT) The compound of formula II) was investigated under laboratory conditions for its potential protective effect as an antioxidant by measuring the oxidation induction time.

[0152] For this purpose, the compound of formula II) and 6 - PPD were each heated at a constant temperature (180 °C) until the start of oxidation together with the polymer (liquid synthetic polyisoprene (IR), LIR - 50, Kuraray, weight - average molecular weight distribution M w = 54000 g / mol, glass transition temperature T g = - 63 °C) (starting temperature 35 °C, heated to 170 °C at a heating rate of 20 K / min (kelvin per minute) and then to 180 °C at a heating rate of 1 K / min; purge gas: nitrogen (N2), volume flow rate 50 ml / min). The test specimens were maintained isothermally at 180 °C for 5 min under a N2 atmosphere and then the atmosphere was switched to an O2 atmosphere (volume flow rate 50 ml / min).

[0153] Oxidation was determined via peaks using DSC (Differential Scanning Calorimetry).

[0154] The time (minutes) to oxidation was measured.

[0155] The results compared to the known anti-aging agent 6-PPD are summarized in Table 2.

[0156]

Table 2

[0157] Taking into account the measurement accuracy of ± (plus / minus) 10 minutes, it is clear that the compound of formula II) achieves a significantly better protective effect because it prolongs the time required for the decomposition of the polymer by oxygen and thus for oxidation. Therefore, the compounds according to the invention of formula I) or formula II) are less harmful to health, more environmentally friendly, and better anti-aging agents than 6-PPD and further representative substances of the substance class as described above. Note that this application relates to the invention described in the claims, but may also include the following as other aspects. 1. Formula I):

Chemical formula

change

change

change

change

Chem.

Chem.

Chem.

Chem.

Chem.

Claims

1. Formula (I): 【Chemical 1】 [wherein, R １ is selected from the group consisting of 1-phenylalkyl groups having a total of 7 to 10 carbon atoms and branched and cyclic C3-C12 alkyl groups, In the formula, R ３ is selected from the group consisting of linear, branched and cyclic C1-C12 alkyl groups and aryl groups, where n takes a value of 0 or 1 or 2 or 3 or 4, and where n is 2 or 3 or 4, the groups R ３ are, independently of one another, identical or different, In the formula, R ２ is selected from the group consisting of linear, branched and cyclic C1-C12 alkyl groups and aryl groups, wherein m takes a value of 0 or 1 or 2 or 3, and wherein when m is 2 or 3, the group R ２ are, independently of one another, identical or different] compound.

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

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

4. R １ The compound according to claim 1 or 2, characterized in that it is bonded to a nitrogen atom (N) via a tertiary carbon atom.

5. R １ is a branched alkyl group having 3 to 12 carbon atoms or a 1-phenylalkyl group having a total of 7 to 10 carbon atoms, and the compound according to claim 1 or 2, characterized in that.

6. R １ The compound according to claim 1 or 2, wherein R is selected from the group consisting of 1,3-dimethylbutyl, 1-phenylethyl and cyclohexyl groups.

7. Formula (II): [Chemical Formula 2] The compound according to claim 1 or 2, characterized by having the structure of.

8. Use of the compound according to claim 1 or 2 as an anti-aging stabilizer in vehicle tires, air springs, bellows, conveyor belts, belts, drive belts, hoses, rubber bands, profiles, seals, membranes, medical or robotic tactile sensors, shoe soles or parts thereof, oils, or lubricants.

9. Use of the compound according to claim 1 or 2 as a dye in fibers or polymers or paper or (decorative) paints or coatings.

10. The following process steps: a1) Providing a compound of formula (A1): 【Chemical Formula 3】 step; b1) Reacting the compound of formula (A1) with a base to obtain a compound of formula (B1): 【Chemical Formula 4】 step; c1) Reacting the compound of formula (B1) with hydrogen or a hydrogenation reagent and a ketone or aldehyde to obtain a compound of formula (I): 【Chemical Formula 5】 step A process for preparing a compound of formula (I) comprising In the formula, R １ is selected from the group consisting of 1-phenylalkyl groups having a total of 7 to 10 carbon atoms and branched and cyclic C3-C12 alkyl groups, In the formula, R ３ is selected from the group consisting of linear, branched and cyclic C1-C12 alkyl groups and aryl groups. In the formula, n takes a value of 0 or 1 or 2 or 3 or 4. In the formula, 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 selected from the group consisting of linear, branched and cyclic C1-C12 alkyl groups and aryl groups, wherein m takes a value of 0 or 1 or 2 or 3, and wherein when m is 2 or 3, the group R ２ is, independently of one another, identical or different, wherein X is halogen, method.

11. The reaction in step c1) of hydrogen with 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 another pressure reactor. The method according to claim 10, characterized in that.

12. At least the following process steps: a2) Providing a compound of formula (A2): 【Chemical Formula 6】 step and; b2) Providing a compound of formula (B2): 【Chemical Formula 7】 step and; c2) Reacting the compound of formula (A2) with the compound of formula (B2) in the presence of a halogenating agent to obtain a compound of formula (C2): 【Chemical 8】 step and; d2) Reacting the compound of formula (C2) in the presence of an acid to obtain a compound of formula (B1): 【Chemical Formula 9】 step and; e2) Reacting the compound of formula (B1) with hydrogen or a hydrogenating agent and a ketone or aldehyde to obtain a compound of formula (I): 【Chemical Formula 10】 step and A process for preparing a compound of formula (I) comprising In the formula, R １ is selected from the group consisting of 1-phenylalkyl groups having a total of 7 to 10 carbon atoms and branched and cyclic C3-C12 alkyl groups, In the formula, R ３ is selected from the group consisting of linear, branched and cyclic C1-C12 alkyl groups and aryl groups. In the formula, n takes a value of 0 or 1 or 2 or 3 or 4. When n is 2 or 3 or 4 in the formula, the groups R ３ are, independently of one another, identical or different. In the formula, R ２ is selected from the group consisting of linear, branched and cyclic C1-C12 alkyl groups and aryl groups, wherein m takes a value of 0 or 1 or 2 or 3, and when m is 2 or 3 in the formula, the group R ２ are, independently of one another, the same or different, wherein X is halogen, method.

13. The process according to claim 12, characterized in that the reaction of hydrogen with the aldehyde or ketone in step e2) is carried out at a temperature of 50 °C to 70 °C using a hydrogenation catalyst, the reaction mixture is subjected to hydrogen at a pressure of 15 to 25 bar, and the reaction is carried out in an autoclave or another pressure reactor.

14. A rubber mixture containing the compound according to claim 1 or 2, the rubber mixture containing at least one diene rubber.

15. A rubber mixture according to claim 14, containing 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.

16. A vehicle tire containing the rubber mixture according to claim 14 in at least one component.

17. A vehicle tire containing the rubber mixture according to claim 14 in at least one outer component, the outer component being a tread, a sidewall and / or a flange profile.

Images