EP4508036A1 - Composé, sa préparation et son utilisation dans des mélanges de caoutchouc et pneus de véhicule, en tant qu'agent anti-vieillissement, antioxydant et/ou agent colorant - Google Patents

Composé, sa préparation et son utilisation dans des mélanges de caoutchouc et pneus de véhicule, en tant qu'agent anti-vieillissement, antioxydant et/ou agent colorant

Info

Publication number
EP4508036A1
EP4508036A1 EP23715022.2A EP23715022A EP4508036A1 EP 4508036 A1 EP4508036 A1 EP 4508036A1 EP 23715022 A EP23715022 A EP 23715022A EP 4508036 A1 EP4508036 A1 EP 4508036A1
Authority
EP
European Patent Office
Prior art keywords
radicals
rubber
compound according
formula
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23715022.2A
Other languages
German (de)
English (en)
Inventor
Andreas Jacob
David-Raphael DAUER
Julian STROHMEIER
Anna-Lena Dreier
Frank Fleck
Carla Recker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Continental Reifen Deutschland GmbH
Original Assignee
Continental Reifen Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Continental Reifen Deutschland GmbH filed Critical Continental Reifen Deutschland GmbH
Publication of EP4508036A1 publication Critical patent/EP4508036A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
    • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
    • C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
    • C07D243/38—[b, e]- or [b, f]-condensed with six-membered rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

Definitions

  • the invention relates to a compound, a rubber mixture containing the compound, a vehicle tire which has the rubber mixture in at least one component, a method for producing the compound and the use of the compound as an anti-aging agent and/or antioxidant and/or dye.
  • Natural rubber, synthetic polymers such as IR, BR, SSBR, ESBR, etc.
  • natural and synthetic oils, fats and lubricants are subject to oxidation reactions that are detrimental when stored for a long time and especially in the target application, which often takes place at higher temperatures affect the original desired properties.
  • the polymer chains are shortened, causing the material to liquefy, or the material is subsequently hardened.
  • Anti-aging agents therefore make a significant contribution to the longevity of vehicle tires and other technical rubber items.
  • aromatic amines such as 6PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine), IPPD (N-isopropyl-N'-phenyl-p-phenylenediamine) or
  • SPPD N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine.
  • These molecules can react with oxygen or ozone or radicals formed, such as alkyl, alkoxy and alkyl peroxy radicals, thus trapping them and thus protecting the polymers from further oxidation reactions.
  • Anti-aging agents that react in particular with ozone and intercept it are also referred to as “ozone inhibitors” or “antiozonants”.
  • Another problem associated with anti-aging agents is that of undesirable blooming. Due to their poor solubility in the surrounding polymer matrix of the rubber article, molecules of the anti-aging agent diffuse to the surface of the article to be protected and form a film there that can usually be distinguished in color from the rest of the article. In the case of vehicle tires, this usually manifests itself in a brown discoloration of the otherwise black sidewall. In addition to the aesthetic disadvantages, this also entails disadvantages in terms of the anti-aging effect. Most of the time, bloomed substances are removed. On the one hand, this reduces the total amount of anti-aging agent and, on the other hand, it causes further molecules of the anti-aging agent to diffuse, so that the polymers are less and less protected.
  • the invention is based on the object of providing a novel compound which can be used in particular as an anti-aging agent in vehicle tires or other technical rubber articles, with a lower risk potential and sufficient solubility in the respective matrix, for example and in particular in the polymer. This is intended to ensure continued optimal protection against oxygen and ozone while reducing the health hazard and to keep or prevent the tendency to blooming as low as possible.
  • the object is achieved by the method according to the invention for producing the compound according to the invention.
  • the compound according to claim 1 has the general formula I): where R 1 is selected from the group consisting of xi) aromatic radicals, the aromatic radicals optionally having substituents which are selected from the group consisting of halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals and Thioether radicals, and xii) linear, branched and cyclic aliphatic C3 to C-12 radicals, where the radicals R 2 and R 3 can independently be the same or different and are selected from the group consisting of linear, branched and cyclic, saturated and unsaturated, aliphatic Ci to C-12 radicals, which optionally carry one or more halogen substituents, aryl radicals, which optionally carry one or more halogen substituents, and halogen radicals, wherein fluorine, bromine and chlorine are preferred, cyano residues, ester residues, ketone residues, ether residues and thioether residues; and where m takes the value
  • C3 to C-12 residues mean that residues with 3 to 12 carbon atoms are meant.
  • Ci is used to designate the position of the most highly oxidized carbon atom or the highest priority according to the Cahn-Ingold-Prelog Convention (CIP). It is clear to the expert in the respective context what is meant.
  • the compound according to the invention is a dibenzodiazepinone derivative and has a lower risk potential compared to known anti-aging agents based on aniline (possible cleavage product of 6PPD).
  • the compound according to the invention has improved oxidation protection compared to the known anti-aging agent 6PPD, especially at higher temperatures of more than 150 ° C, which means that the compound according to formula I) has a comparable or even improved protective effect, especially in vehicle tires and other technical rubber articles, but also in oils and lubricants.
  • the invention should not be tied to a specific mechanism of action or a specific explanation.
  • the compound according to the invention is therefore suitable as a replacement for 6PPD, the degradation products of which are extremely toxic for coho salmon and therefore also for other aquatic organisms.
  • the compound according to the invention also has sufficient solubility in rubber mixtures, in particular for vehicle tires and other technical rubber articles. This minimizes the blooming of this compound, as is known from many anti-aging agents, which in turn has a beneficial effect on the anti-aging effect.
  • the compound according to the invention according to formula I) is particularly suitable as an anti-aging agent and/or anti-ozone agent in vehicle tires and/or other technical rubber articles, such as in particular an air spring, a bellows, a conveyor belt, a belt, a hose, a rubber band, a profile, a seal, a membrane, tactile sensors for medical applications or robotic applications, or a shoe sole or parts thereof, and/or oils and/or lubricants.
  • the compound according to the invention according to formula I) is particularly suitable for producing a rubber article, in particular an air spring, a bellows, a conveyor belt, a belt, a hose, a rubber band, a profile, a seal, a membrane, tactile sensors for medical applications or robotic applications, or a shoe sole or parts thereof.
  • the compound according to formula I) is used in a composition and mixed into it.
  • this is in particular a rubber mixture.
  • a further subject of the invention is the use of the compound according to the invention according to formula I) in oils, lubricants, such as in particular fuels or operating fluids for engines.
  • the compound according to the invention can therefore be used in engines.
  • a further subject of the invention is the use of the compound according to the invention according to formula I) as a dye in fibers and/or polymers and/or paper and/or in (coating) paints and varnishes.
  • the invention includes all advantageous embodiments, which are reflected, among other things, in the patent claims.
  • the invention also includes embodiments that result from the combination of different features of different gradations in the preference for these features, so that a combination of a first feature designated as “preferred” or described in the context of an advantageous embodiment with another feature as e.g. B. “particularly preferred” feature is included in the invention.
  • the group -N(H)R 1 is preferably arranged in the meta position to X.
  • the compound according to the invention therefore preferably has the structure according to formula II): where R 1 , R 2 , R 3 , X and Y as well as m and n are as defined above.
  • X is, such as B. recognizable in formulas I) and II), integrated into the ring structure and selected from 0 (oxygen atom), S (sulfur atom) and N (H) (secondary amino group).
  • X is each equal to NH.
  • Y is, such as B. recognizable in formulas I) and II), terminally bound to the carbon atom and selected from 0 (oxygen atom), S (sulfur atom) and N (H) (secondary amino group).
  • the object on which the invention is based is achieved particularly well, with very good oxidation protection being achieved in polymers and/or rubber mixtures, in particular for vehicle tires.
  • the radicals R 2 and R 3 are independently the same or different and are selected from the group consisting of linear, branched and cyclic, saturated and unsaturated, aliphatic Ci to C-12 radicals, which optionally carry one or more halogen substituents, aryl radicals, which optionally carry one or more halogen substituents, and halogen radicals, wherein fluorine, bromine and Chlorine is preferred, cyano residues, ester residues, ketone residues, ether residues and thioether residues.
  • radicals R 2 and R 3 mentioned can already be bound to the respective benzene ring or its precursor, in particular through the selection of suitable starting substances.
  • m is equal to zero (0).
  • n is equal to zero (0).
  • X is preferably N(H) and Y is 0.
  • the radical R 1 is selected from the group consisting of xi) aromatic residues, the aromatic residues optionally carrying substituents selected from the group consisting of halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether residues, and xii) linear , branched and cyclic aliphatic C3 to C-12 residues.
  • the aromatic radical from subgroup xi) is, for example and preferably selected from phenyl radicals (-CßHs) and benzyl radicals (-CH2-C6H5), with phenyl being particularly preferred.
  • the aromatic residues of subgroup xi) can carry substituents. As stated above, these are selected from the group consisting of halogen residues, cyano residues, ester residues, ketone residues, ether residues and thioether residues.
  • the substituents are preferably selected from the group consisting of ester residues, ketone residues, ether residues and thioether residues.
  • the aromatic radical is not substituted on the two C atoms that are adjacent to the C-i atom, i.e. the carbon atom that is bonded to the N atom.
  • the aromatic radical is therefore preferably no substituent in the o/trio position to the N atom.
  • the aromatic residue of subgroup xi) is unsubstituted.
  • R 1 is bonded to the nitrogen atom (N) via a tertiary carbon atom.
  • the Ci atom is therefore preferably a tertiary carbon atom.
  • tertiary carbon atom means a carbon atom that is bonded to only one hydrogen atom.
  • R 1 in particular in the above-mentioned formulas I), II), la), Ha), is a branched or cyclic alkyl radical with three to twelve carbon atoms, preferably three to eight carbon atoms, where R 1 is particularly preferably selected from 1,3-dimethylbutyl and
  • R 1 is very particularly preferably a 1,3-dimethylbutyl radical.
  • the compound according to the invention has the structure according to formula III):
  • the compound according to formula III) has sufficient solubility in polymers, in particular in rubber mixtures for vehicle tires and other technical rubber articles.
  • the compound according to formula II) can be produced particularly easily and in an energy and cost-saving manner and shows a comparable or even improved performance compared to 6PPD
  • a further subject of the present invention is a process for producing the compound according to formula I), which comprises at least the following process steps: i) producing or providing the substance according to formula B1): ii) reaction of the compound according to formula B1) with hydrogen and a ketone or aldehyde, preferably ketone, to give the compound according to formula I): where R 1 is selected from the group consisting of xi) aromatic radicals, the aromatic radicals optionally having substituents which are selected from the group consisting of halogen radicals, cyano radicals, ester radicals, ketone radicals, ether radicals and Thioether radicals, and xii) linear, branched and cyclic aliphatic C3 to C-12 radicals, where the radicals R 2 and R 3 can independently be the same or different
  • the compound according to formula B1) can be prepared for X equal to N(H) (secondary amino group) and Y equal to 0 (oxygen atom), for example analogously to US 6919328 according to the following scheme S1): where TEA stands for triethylamine and DMSO stands for dimethyl sulfoxide.
  • the group -N(H)R 1 or, in the starting substance, the group -NO2 is preferably arranged in the meta position to X, as already explained above.
  • the compound produced according to the invention therefore preferably has the structure according to formula II):
  • the starting substance according to formula B1) preferably has the structure according to formula B1 a):
  • X is N(H) and Y is 0.
  • a suitable catalyst referred to as a “hydrogenation catalyst” in the context of the present invention, is preferably used in the reaction with hydrogen in step ii).
  • the hydrogenation catalyst is preferably a noble metal catalyst, such as in particular palladium (Pd) or platinum (Pt). Preference is given to using the noble metal on carbon (C), such as palladium on carbon (Pd/C).
  • the reaction in step ii) is particularly preferably carried out with hydrogen, using a hydrogenation catalyst.
  • the reaction in step ii) preferably takes place at a temperature of 50 to 130 °C, preferably 50 to 100 °C, particularly preferably 50 to 80 °C, in particular, for example, 60 °C.
  • Hydrogen is preferably pressed in at a pressure of 30 to 70 bar, particularly preferably 35 to 45 bar, in particular, for example, 40 bar, and then preferably for 1 to 20 hours, preferably 3 to 13 hours, particularly preferably 5 to 13 hours, in particular for Example 10 hours, stirred.
  • the reaction with hydrogen in step ii) preferably takes place in a container suitable for the preferably comparatively high pressure, such as in particular in an autoclave or in another pressure reactor.
  • the reaction in step ii) is particularly preferably carried out with hydrogen using a hydrogenation catalyst and at a temperature of 50 to 130 ° C, preferably 50 to 100 ° C, particularly preferably 50 to 80 ° C, and hydrogen at a pressure of 30 to 70 bar, particularly preferably 35 to 45 bar, especially for example 40 bar, is applied and the reaction takes place in an autoclave or in another pressure reactor.
  • the ketone in step ii) is the ketone derivative of the later radical R 1 ;
  • R 1 For an aldehyde, it is the aldehyde derivative.
  • the solvent in step ii) can be either the ketone or aldehyde when in liquid form, or an inert solvent such as toluene or xylene, particularly when the ketone or aldehyde is in solid form. In the latter case, the ketone or aldehyde is used as a reactant only in stoichiometric amounts.
  • a ketone or aldehyde R 1 O, particularly preferably ketone, is preferably used in liquid form as a solvent. This means that there is no need for an additional substance such as toluene or xylene.
  • Purification is preferably carried out following step ii), for example by filtration and washing with a solvent, in particular ethanol, and/or by column chromatography, for example on silica gel or by recrystallization from cyclohexane or higher-chain aliphatics.
  • a solvent in particular ethanol
  • column chromatography for example on silica gel or by recrystallization from cyclohexane or higher-chain aliphatics.
  • Another subject of the invention is, as stated above, a rubber mixture.
  • the rubber mixture according to the invention contains the compound according to formula I), for example and preferably the compound according to formula III).
  • the rubber mixture according to the invention can in principle be any rubber mixture, in particular in which the novel compound according to the invention according to formula I) or III) acts as an anti-aging agent and/or anti-ozone agent with lower toxicity.
  • the rubber mixture according to the invention contains at least one rubber.
  • the rubber mixture according to the invention preferably contains 0.1 to 10 phr, particularly preferably 0.1 to 7 phr, very particularly preferably 1 to 6 phr, again preferably 1 to 3 phr, of the compound according to formula I), for example and preferably the compound according to formula III).
  • the rubber mixture can also contain a mixture of several compounds that fall under formula I).
  • the specification phr (parts per hundred parts of rubber by weight) used in this document is the usual quantity specification for mixture recipes in the rubber industry.
  • the dosage of the parts by weight of the individual substances is set in this document to 100 parts by weight of the total mass of all in the Mixture of existing high molecular weight (M w greater than 20,000 g / mol) rubbers.
  • the rubber mixture according to the invention contains at least one diene rubber.
  • the rubber mixture can therefore contain a diene rubber or a mixture of two or more different diene rubbers.
  • the diene rubber is preferably selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), epoxidized polyisoprene (ENR), butadiene rubber (BR), butadiene-isoprene rubber, solution-polymerized styrene-butadiene rubber (SSBR ), emulsion-polymerized styrene-butadiene rubber (ESBR), styrene-isoprene rubber, liquid rubbers with a molecular weight M w of greater than 20,000 g/mol, halobutyl rubber, polynorbornene, isoprene-isobutylene copolymer, ethylene-propylene-diene Rubber, nitrile rubber, chloroprene rubber, acrylate rubber, fluorine rubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-butad
  • nitrile rubber, hydrogenated acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber and/or ethylene-propylene-diene rubber are used in the production of technical rubber articles, such as belts, straps and hoses, and/or shoe soles.
  • the mixture compositions known to those skilled in the art for these rubbers - which are special with regard to fillers, plasticizers, vulcanization systems and additives - are preferred.
  • the natural and/or synthetic polyisoprene of all embodiments can be both cis-1,4-polyisoprene and 3,4-polyisoprene.
  • cis-1,4-polyisoprene with a cis-1,4 proportion > 90% by weight is preferred.
  • such a polyisoprene can be obtained by stereospecific polymerization in solution with Ziegler-Natta catalysts or using finely divided lithium alkyls.
  • natural rubber (NR) is a cis-1,4 polyisoprene in which the cis-1,4 content in the natural rubber is greater than 99% by weight.
  • natural rubber is understood to mean naturally occurring rubber that can be obtained from Hevea rubber trees and “non-Hevea” sources.
  • Non-Hevea sources include guayule bushes and dandelions such as TKS (Taraxacum kok-saghyz; Russian dandelion).
  • a low-cis polybutadiene is, for example, Li-BR (lithium-catalyzed butadiene rubber) with a cis content of 20 to 50% by weight. With a high-cis BR, particularly good properties and low hysteresis of the rubber mixture are achieved.
  • the polybutadiene(s) used can be end group modified with modifications and functionalizations and/or functionalized along the polymer chains.
  • the modification can be those with hydroxy groups and/or ethoxy groups and/or epoxy groups and/or siloxane groups and/or amino groups and/or aminosiloxane and/or carboxy groups and/or phthalocyanine -Groups and/or silane sulfide groups act.
  • other modifications known to those skilled in the art, also referred to as functionalizations also come into consideration.
  • Metal atoms can be part of such functionalizations.
  • styrene-butadiene rubber styrene-butadiene copolymer
  • SSBR solution-polymerized styrene-butadiene rubber
  • ESBR emulsion-polymerized styrene-butadiene rubber
  • the styrene-butadiene copolymer used can be end-group modified and/or functionalized along the polymer chains with the modifications and functionalizations mentioned above for polybutadiene.
  • the at least one diene rubber is 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 (HR) and halobutyl rubber.
  • natural polyisoprene NR, natural rubber
  • synthetic polyisoprene IR
  • butadiene rubber BR
  • solution-polymerized styrene-butadiene rubber SSBR
  • ESBR emulsion-polymerized styrene-butadiene rubber
  • HR butyl rubber
  • halobutyl rubber halobutyl rubber
  • 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 rubber.
  • NR natural polyisoprene
  • IR synthetic polyisoprene
  • BR butadiene rubber
  • SSBR solution-polymerized styrene-butadiene rubber
  • ESBR Butadiene rubber
  • the rubber mixture contains at least one natural polyisoprene (NR), preferably in amounts of 50 to 100 phr, and according to a particularly advantageous embodiment of the invention 80 to 100 phr, very particularly preferably 95 to 100 phr, again preferably 100 phr.
  • NR natural polyisoprene
  • the rubber mixture contains less than 100 phr NR, it preferably contains as an additional rubber at least one diene rubber, which is selected from the group consisting of synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber. rubber (SSBR) and emulsion polymerized styrene-butadiene rubber (ESBR).
  • IR synthetic polyisoprene
  • BR butadiene rubber
  • SSBR solution-polymerized styrene-butadiene rubber
  • ESBR emulsion polymerized styrene-butadiene rubber
  • the rubber mixture contains at least one natural polyisoprene (NR), preferably in amounts of 5 to 55 phr, and according to a particularly advantageous embodiment of the invention 5 to 25 phr, very particularly preferably 5 to 20 phr.
  • NR natural polyisoprene
  • the rubber mixture contains at least one polybutadiene (BR, butadiene rubber), preferably in amounts of 10 to 80 phr, particularly preferably 10 to 50 phr, and according to a particularly advantageous embodiment of the invention 15 to 40 phr.
  • BR polybutadiene
  • the rubber mixture contains at least one polybutadiene (BR, butadiene rubber), preferably in amounts of 10 to 80 phr, particularly preferably 10 to 50 phr, and according to a particularly advantageous embodiment of the invention 15 to 40 phr.
  • the rubber mixture contains at least one solution-polymerized styrene-butadiene rubber (SSBR), preferably in amounts of 10 to 80 phr, particularly preferably 30 to 80 phr, and according to a particularly advantageous embodiment of the invention 50 to 70 p.m.
  • SSBR solution-polymerized styrene-butadiene rubber
  • the rubber mixture preferably contains at least one filler, preferably in amounts of 30 to 500 phr, particularly preferably 50 to 400 phr, again preferably 80 to 300 phr.
  • the filler is a reinforcing filler, which is preferably selected from the group consisting of carbon black and silicon dioxide.
  • carbon blacks All types of soot known to those skilled in the art can be used as carbon blacks.
  • the carbon black is preferably selected from industrial carbon blacks and pyrolysis carbon blacks, with industrial carbon blacks being further preferred.
  • the carbon black preferably has an iodine number, according to ASTM D 1510, which is also referred to as the iodine adsorption number, between 30 and 250 g/kg, preferably 30 to 180 g/kg, particularly preferably 40 to 180 g/kg, and very particularly preferably 40 to 130 g/kg, and a DBP number according to ASTM D 2414 of 30 to 200 ml/100 g, preferably 70 to 200 ml/100g, particularly preferably 90 to 200 ml/100g.
  • ASTM D 1510 which is also referred to as the iodine adsorption number
  • the DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light filler using dibutyl phthalate.
  • Particularly suitable and preferred is a carbon black with an iodine adsorption number between 80 and 110 g/kg and a DBP number of 100 to 130 ml/100g, such as in particular carbon black of type N339.
  • the silicon dioxide is preferably amorphous silicon dioxide, for example precipitated silica, which is also referred to as precipitated silicon dioxide.
  • precipitated silicon dioxide Alternatively, for example, pyrogenic silicon dioxide can also be used.
  • a finely divided, precipitated silica which has a nitrogen surface (BET surface) (according to DIN ISO 9277 and DIN 66132) of 35 to 400 m 2 /g, preferably from 35 to 350 m 2 /g, particularly preferably from 85 to 320 m 2 /g and very particularly preferably from 120 to 235 m 2 /g, and a CTAB surface (according to ASTM D 3765) from 30 to 400 m 2 /g, preferably from 30 to 330 m 2 /g, particularly preferably from 80 to 300 m 2 /g and very particularly preferably from 115 to 200 m 2 /g.
  • BET surface nitrogen surface
  • CTAB surface accordinging to ASTM D 3765
  • the vulcanizates have particularly good physical properties.
  • Silicas can therefore be used, for example: B. both those of the type Ultrasil® VN3 (trade name) from Evonik as well as highly dispersible silicas, so-called HD silicas (e.g. Zeosil® 1165 MP from Solvay), can be used.
  • the rubber mixture contains at least one silica as a filler, preferably in amounts of 30 to 500 phr, particularly preferably 50 to 400 phr, again preferably 80 to 300 phr.
  • These amounts contain silica, in particular as the sole or main filler (more than 50% by weight based on the total amount of filler).
  • the rubber mixture contains at least one silica as a further filler, preferably in amounts of 5 to 100 phr, particularly preferably 5 to 80 phr, again preferably 10 to 60 phr.
  • silica is included in particular as a further filler in addition to another main filler, such as in particular a carbon black.
  • silicic acid and “silica” are used synonymously in the context of the present 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, very particularly preferably 5 to 15 phr, at least one soot.
  • carbon black is included in particular as a further filler in addition to a main filler, such as, in particular, silica.
  • the rubber mixture according to the invention contains 30 to 300 phr, preferably 30 to 200 phr, particularly preferably 40 to 100 phr of at least one carbon black. These amounts contain carbon black as the sole or main filler and possibly in combination with silica in the smaller amounts mentioned above.
  • the rubber mixture contains 5 to 60 phr, particularly preferably 5 to 40 phr, of at least one carbon black and 50 to 300 phr, preferably 80 to 200 phr of at least one silica.
  • the rubber mixture can also contain other fillers that have a reinforcing effect or do not have a reinforcing effect.
  • non-reinforcing fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide or rubber gels as well as fibers (such as aramid fibers, glass fibers, carbon fibers, cellulose fibers).
  • CNT carbon nanotubes
  • HCF hollow carbon fibers
  • modified CNT containing one or more functional groups such as hydroxy, carboxy and carbonyl groups
  • graphite and graphene so-called “carbon-silica dual-phase filier”.
  • Zinc oxide is not one of the fillers in the context of the present invention.
  • the rubber mixture can contain customary additives in customary parts by weight, which are preferably added in at least one basic mixing stage during its production.
  • additives include a) anti-aging agents known in the prior art, such as B. p-phenylenediamines, such as
  • N-Phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD),
  • SPPD N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine
  • DTPD N,N'-ditolyl-p-phenylenediamine
  • stearic acid and / or other activators, such as zinc complexes such as zinc ethyl hexanoate, c) activators and / or agents for the binding of fillers, in particular carbon black or silica, such as S-(3-aminopropyl )Thiosulfuric acid and / or its metal salts (binding to soot) and silane coupling agents (binding to silicon dioxide, in particular silicic acid), d) ozone protection waxes, e) resins, in particular adhesive resins, f) mastication aids, such as. B.
  • activators such as zinc complexes such as zinc ethyl hexanoate
  • activators and / or agents for the binding of fillers in particular carbon black or silica, such as S-(3-aminopropyl )Thiosulfuric acid and / or its metal salts (binding to soot) and silane coupling agents (binding to
  • 2,2'-dibenzamidiphenyl disulfide (DBD) and g) process aids, such as in particular fatty acid esters and metal soaps, such as zinc soaps and / or calcium soaps h) plasticizers, such as in particular aromatic, naphthenic or paraffinic mineral oil plasticizers, such as MES (mild extraction solvate ) or RAE (Residual Aromatic Extract) or TDAE (treated distillate aromatic extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid oils (BTL) preferably with a polycyclic aromatic content of less than 3 % by weight according to method IP 346 or triglycerides, such as. B. rapeseed oil, or facts or hydrocarbon resins or liquid polymers whose average molecular weight (determined by GPC gel permeation chromatography, based on BS ISO 11344:2004) is between 500 and 20,000 g/mol.
  • plasticizers such as in particular aromatic, naphthenic
  • the rubber mixture according to the invention contains, in addition to the compound according to the invention according to formula I), for example according to formula III), no anti-aging agents from the group of p-phenylenediamines, in particular those in list a).
  • the rubber mixture according to the invention contains 0 to 0.1 phr, in particular 0 phr, of further anti-aging agents based on p-phenylenediamines, which are selected from the group containing, preferably consisting of, N-phenyl-N'- (1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine (SPPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N 'N'-Ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD) .
  • p-phenylenediamines which are selected from the group
  • the compound according to the invention according to formula I), for example according to formula III replaces the p-phenylenediamines mentioned in the prior art.
  • At least one further of the p-phenylenediamine anti-aging agents mentioned is included, so that the compound according to the invention only partially replaces the p-phenylenediamines known in the prior art.
  • the advantage according to the invention is also achieved, just not to an optimal extent.
  • anti-aging agents based on dihydroquinoline such as TMQ
  • TMQ dihydroquinoline
  • the amount of dihydroquinolines contained, such as in particular TMQ, is preferably 0.1 to 3, in particular 0.5 to 1.5 phr.
  • Ozone protection waxes (group d above) are considered separately and, according to preferred embodiments of the invention, are contained in the rubber mixture, regardless of whether additional anti-aging agents a) are included.
  • the silane coupling agents can be any type known to those skilled in the art.
  • one or more different silane coupling agents can be used in combination with one another.
  • the rubber mixture can therefore contain a mixture of different silanes.
  • silane coupling agents react with the surface silanol groups of the silicon dioxide, in particular the silica, or other polar groups during the mixing of the rubber or the rubber mixture (in situ) or before the filler is added to the rubber in the sense of a pretreatment (premodification).
  • Coupling agents known from the prior art are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group on the silicon atom as a leaving group and which, as other functionality, have a group which, after cleavage, can optionally enter into a chemical reaction with the double bonds of the polymer.
  • silane coupling agents can be used: B. 3-mercaptopropyltriethoxysilane, 3-thiocyanato-propyltrimethoxysilane or 3,3'-bis (triethoxysilylpropyl) polysulfides with 2 to 8 sulfur atoms, such as. B. 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT), the corresponding disulfide (TESPD) or mixtures of the sulfides with 1 to 8 sulfur atoms with different contents of the different sulfides can be used.
  • TESPT can also be added as a mixture with industrial carbon black (trade name X50S® from Evonik).
  • Blocked mercaptosilanes such as those found e.g. B. are known from WO 99/09036, can be used as a silane coupling agent.
  • silanes as described in WO 2008/083241 A1, WO 2008/083242 A1, WO 2008/083243 A1 and the WO 2008/083244 A1 are described can be used.
  • the proportion of the total amount of further additives is preferably 3 to 150 phr, particularly preferably 3 to 100 phr and very particularly preferably 5 to 80 phr.
  • the total amount of other additives may contain zinc oxide (ZnO) in the amounts mentioned above.
  • the conventionally used zinc oxide generally has a BET surface area of less than 10 m 2 /g.
  • a zinc oxide with a BET surface area of 10 to 100 m 2 /g such as so-called “nano-zinc oxides”, can also be used.
  • the rubber mixture according to the invention is preferably used vulcanized, in particular in vehicle tires or other vulcanized technical rubber articles.
  • the vulcanization of the rubber mixture according to the invention is preferably carried out in the presence of sulfur and/or sulfur donors with the aid of vulcanization accelerators, whereby some vulcanization accelerators can also act as sulfur donors.
  • the accelerator is selected from the group consisting of thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate accelerators and guanidine accelerators.
  • a sulfenamide accelerator which is selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazyl-2-sulfenmorpholide (MBS), N- tert-Butyl-2-benzothiazylsulfenamide (TBBS) and guanidine accelerators such as diphenylguanidine (DPG).
  • CBS N-cyclohexyl-2-benzothiazolesufenamide
  • DCBS N,N-dicyclohexylbenzothiazole-2-sulfenamide
  • MFS benzothiazyl-2-sulfenmorpholide
  • TBBS N- tert-Butyl-2-benzothiazylsulfenamide
  • DPG diphenylguanidine
  • vulcanization retarders may be present in the rubber mixture.
  • the production of the rubber mixture is preferably carried out using the process common in the rubber industry, in which a basic mixture with all components except the vulcanization system (e.g. sulfur and substances influencing vulcanization) is first produced in one or more mixing stages.
  • the finished mixture is created by adding the vulcanization system in a final mixing stage.
  • the finished mixture is further processed, for example, by an extrusion process or calendering and brought into the appropriate shape.
  • the rubber mixture according to the invention is particularly suitable for use in vehicle tires, in particular pneumatic vehicle tires.
  • vehicle tires in particular pneumatic vehicle tires.
  • the application is conceivable in all tire components, in particular in an outer component, in particular and preferably in the horn profile, tread and/or the sidewall tread.
  • the rubber mixture according to the invention is preferably used at least in the cap.
  • the mixture is brought into the appropriate shape, preferably an outer component, as a ready-made mixture before vulcanization and applied in the known manner during the production of the vehicle tire blank.
  • the rubber mixture according to the invention for use as another body mixture in vehicle tires is produced as already described. The difference lies in the shaping after the extrusion process or calendering of the mixture. The resulting forms of the still unvulcanized rubber mixture for one or more different body mixtures are then used to build a green tire.
  • body mixture refers to the rubber mixtures for the inner components of a tire, such as essentially squeegee, inner liner (inner layer), core profile, belt, shoulder, belt profile, carcass, bead reinforcer, bead profile, horn profile and bandage.
  • the still unvulcanized tire blank is then vulcanized.
  • the extruded, still unvulcanized mixture is brought into the appropriate shape and, during or afterward, is often provided with strength carriers, for example synthetic fibers or steel cords.
  • strength carriers for example synthetic fibers or steel cords.
  • Another object of the present invention is a vehicle tire which has the rubber mixture according to the invention containing the compound according to the invention in at least one component.
  • the vulcanized vehicle tire has a vulcanizate of at least one rubber mixture according to the invention in at least one component. It is known to those skilled in the art that most substances, such as. B. the rubbers contained are or can be present in a chemically modified form either after mixing or only after vulcanization.
  • vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction site vehicles, truck, car and bicycle tires.
  • the vehicle tire according to the invention preferably has the rubber mixture according to the invention in at least one outer component, the outer component preferably being a tread, a sidewall and/or a horn profile.
  • the vehicle tire according to the invention can therefore also have the rubber mixture according to the invention containing the compound according to the invention according to formula I) in several components in a possibly adapted composition.
  • the compound according to formula III) was examined for its potential protective effect as an anti-aging agent by measuring the oxidation-induction time under laboratory conditions.
  • the sample was kept isothermally at 180°C under an N2 atmosphere for 5 minutes and then switched to an O2 atmosphere (with a volume flow of 50 mL/min).
  • Heating to 165 °C was carried out analogously, with first heating to 155 °C with a heating rate of 20 K/min (Kelvin per minute) and then heating to 165 °C with a heating rate of 1 K/min.
  • Heating to 150 °C was carried out analogously, with first heating to 140 °C with a heating rate of 20 K/min (Kelvin per minute) and then heating to 150 °C with a heating rate of 1 K/min.
  • the oxidation was determined via a peak using DSC (differential scanning calorimetry).
  • the compound according to the invention according to formula III) as a representative of the compound according to the invention according to formula I) is therefore more environmentally and health-friendly than 6PPD or other representatives of the substance class, as stated at the beginning, and is also a comparable or even better anti-aging agent.
  • the compound according to the invention according to formula III) as a representative of the compound according to the invention according to formula I) has sufficient solubility in rubber mixtures. This keeps blooming to a minimum, which in turn has a beneficial effect on the protective effect.
  • the compound according to formula III) is mixed in, for example, in various amounts, as shown in Table 2.
  • the resulting examples according to the invention are marked E1 and E2.
  • rubber mixtures containing 6PPD instead of the compound according to formula III) serve as anti-aging agents with otherwise the same composition, with one between V1 and E1 and V2 and E2 mole-equal exchange takes place.
  • the amounts in Table 2 are given in the unit phr. Furthermore, a reference (Ref.) without anti-aging agents is given. For all mixtures, the sum of the amounts of anti-aging agent (6PPD or Formula III) and plasticizer oil MES is 10 phr.
  • the examples according to the invention show a comparable or even improved anti-aging effect compared to rubber mixtures with 6PPD.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

L'invention concerne un composé (I), un mélange de caoutchouc contenant le composé, un pneu de véhicule comprenant le mélange de caoutchouc dans au moins un composant, un procédé de préparation du composé, et l'utilisation du composé en tant qu'agent anti-vieillissement et/ou antioxydant et/ou agent colorant, R1 étant choisi dans le groupe constitué par xi) des groupes aromatiques, les groupes aromatiques portant éventuellement des substituants qui sont choisis dans le groupe constitué par des groupes halogène, des groupes cyano, des groupes ester, des groupes cétone, des groupes éther et des groupes thioéther, et xii) des groupes en C3 à C12 aliphatiques linéaires, ramifiés et cycliques, X étant choisi parmi O (atome d'oxygène), S (atome de soufre) et N(H) (groupe amino secondaire), et Y étant choisi parmi O (atome d'oxygène), S (atome de soufre) et N(H) (groupe amino secondaire).
EP23715022.2A 2022-04-13 2023-03-24 Composé, sa préparation et son utilisation dans des mélanges de caoutchouc et pneus de véhicule, en tant qu'agent anti-vieillissement, antioxydant et/ou agent colorant Pending EP4508036A1 (fr)

Applications Claiming Priority (2)

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DE102022203731.6A DE102022203731A1 (de) 2022-04-13 2022-04-13 Verbindung, Kautschukmischung enthaltend die Verbindung, Fahrzeugreifen, der die Kautschukmischung in wenigstens einem Bauteil aufweist, Verfahren zur Herstellung der Verbindung sowie Verwendung der Verbindung als Alterungsschutzmittel und/oder Antioxidationsmittel und/oder Farbstoff
PCT/DE2023/200064 WO2023198254A1 (fr) 2022-04-13 2023-03-24 Composé, sa préparation et son utilisation dans des mélanges de caoutchouc et pneus de véhicule, en tant qu'agent anti-vieillissement, antioxydant et/ou agent colorant

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US (1) US20250250241A1 (fr)
EP (1) EP4508036A1 (fr)
JP (1) JP2025512332A (fr)
KR (1) KR20240163108A (fr)
CN (1) CN118922410A (fr)
DE (1) DE102022203731A1 (fr)
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Publication number Priority date Publication date Assignee Title
US4829115A (en) * 1988-03-03 1989-05-09 The Goodyear Tire & Rubber Company Organothioethyl alcohol segmers as antidegradant synergists
ATE239737T1 (de) 1997-08-21 2003-05-15 Crompton Corp Blockierte merkaptosilane als kupplungsmittel für gefüllte kautschukzusammensetzung
US6919328B1 (en) 2001-10-09 2005-07-19 Neuraxon Inc. Tricyclic compounds with NOS activity
CA2515790C (fr) * 2003-02-27 2012-11-27 Abbott Laboratories Inhibiteurs de kinase heterocyclique
US7968636B2 (en) 2006-12-28 2011-06-28 Continental Ag Tire compositions and components containing silated cyclic core polysulfides
US7968634B2 (en) 2006-12-28 2011-06-28 Continental Ag Tire compositions and components containing silated core polysulfides
US7968633B2 (en) 2006-12-28 2011-06-28 Continental Ag Tire compositions and components containing free-flowing filler compositions
US7968635B2 (en) 2006-12-28 2011-06-28 Continental Ag Tire compositions and components containing free-flowing filler compositions
JP2010037522A (ja) * 2008-08-08 2010-02-18 Seiko Kagaku Kk バイオディーゼル燃料用酸化防止剤
DE102020212508A1 (de) * 2020-10-02 2022-04-07 Continental Reifen Deutschland Gmbh Verbindung, Kautschukmischung enthaltend die Verbindung, Fahrzeugreifen, der die Kautschukmischung in wenigstens einem Bauteil aufweist, Verfahren zur Herstellung der Verbindung sowie Verwendung der Verbindung als Alterungsschutzmittel und/oder Antioxidationsmittel und/oder Antiozonant und/oder Farbstoff

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KR20240163108A (ko) 2024-11-18
WO2023198254A1 (fr) 2023-10-19
JP2025512332A (ja) 2025-04-17
US20250250241A1 (en) 2025-08-07
CN118922410A (zh) 2024-11-08

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