WO2022048565A1 - Procédé de préparation pour composé p-phénylènediamine substitué par un groupe diaryle asymétrique - Google Patents

Procédé de préparation pour composé p-phénylènediamine substitué par un groupe diaryle asymétrique Download PDF

Info

Publication number
WO2022048565A1
WO2022048565A1 PCT/CN2021/115983 CN2021115983W WO2022048565A1 WO 2022048565 A1 WO2022048565 A1 WO 2022048565A1 CN 2021115983 W CN2021115983 W CN 2021115983W WO 2022048565 A1 WO2022048565 A1 WO 2022048565A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
fecl
reaction
hydroquinone
Prior art date
Application number
PCT/CN2021/115983
Other languages
English (en)
Chinese (zh)
Inventor
邢金国
郭湘云
祁琦
刘燕祥
唐志民
Original Assignee
圣奥化学科技有限公司
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 圣奥化学科技有限公司 filed Critical 圣奥化学科技有限公司
Publication of WO2022048565A1 publication Critical patent/WO2022048565A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7003—A-type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • C07C215/82—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a carbon atom of another six-membered aromatic 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the field of rubber antioxidants, in particular to asymmetric diaryl-substituted p-phenylenediamine compounds and a preparation method thereof.
  • diaryl-substituted p-phenylenediamine has a long-term anti-aging effect.
  • diaryl-p-phenylenediamine is less volatile, resistant to extraction, and has a more durable protective effect.
  • antioxidant H and antioxidant 3100 are typical after-effect long-acting antioxidants, which can supplement the shortcomings of 4010 and 4020 type antioxidants that have good anti-aging effects in the early stage and slightly worse in the later stage.
  • the anti-aging agent H is N,N'-diphenyl-p-phenylenediamine with a symmetrical structure, which has strong crystallinity and poor compatibility with rubber. , causing discoloration and pollution of the tread, and quickly losing the protection against rubber aging. Blooming is a phenomenon in which the liquid or solid compounding agent inside the rubber migrates to the surface and precipitates.
  • Anti-aging agent 3100 is a mixture, of which about 45% is diaryl-p-phenylenediamine with symmetrical structure (23% N,N'-diphenyl-p-phenylenediamine and 22% N,N'-bis(methyl)p-phenylenediamine phenylenediamine), the other 45% is N-phenyl-N'-tolyl-p-phenylenediamine with asymmetric structure, so antioxidant 3100 is also prone to blooming phenomenon, and the dosage is generally not more than 1.5 parts.
  • U.S. Patent Document US3432460 introduces the synthetic method of diaryl-p-phenylenediamine antiaging agent, the preparation of antiaging agent H takes hydroquinone and aniline as reaction raw materials, takes Lewis acid such as anhydrous ferric chloride as catalyst, high temperature micro The positive pressure toluene is refluxed with water, and the amount of water brought out is used as a sign to measure the end of the reaction. After the reaction is completed, the temperature is lowered and a saturated aqueous sodium carbonate solution is added to quench the reaction. Inorganic solidification after cooling. If a mixture of aniline and o-toluidine is reacted with hydroquinone, a three-component mixture, namely antioxidant 3100, is obtained. According to the reaction principle, the one-component asymmetric diaryl-p-phenylenediamine cannot be obtained according to this process.
  • European patent document EP0588060A2 adopts the method of first synthesizing N-alkyl-substituted phenyl-p-phenylenediamine, and then condensing and dehydrogenating it with different alkyl-substituted cyclohexanone to generate asymmetric diaryl-substituted p-phenylenediamine.
  • the alkyl-substituted cyclohexanone is difficult to synthesize, the cost is relatively high, and the hydrogen acceptor needs to be consumed, and a large amount of by-products are easily generated.
  • the US patent document US4804783A adopts the first synthesis of N-alkyl-substituted phenyl-p-phenylenediamine, and then condensation with different alkyl-substituted phenols to prepare the target product.
  • cyclohexanone is required as a hydrogen transfer reagent, the reaction conditions are harsh, and it is not easy to carry out, especially the alkyl-substituted phenol is difficult to react, and the product can hardly be obtained.
  • the present invention provides a new method for preparing asymmetric diaryl-substituted p-phenylenediamine compounds.
  • Asymmetric diaryl-substituted p-phenylenediamine compounds are usually used as anti-aging agents for rubber products, especially rubber tires, which can prevent rubber products or rubber tires from being damaged by light, heat, oxygen, fatigue, etc. during long-term use. Degradation.
  • the method of the invention has the advantages of lower cost, less side reactions, less severe reaction conditions and higher yield.
  • the present invention provides a method for preparing an asymmetric diaryl-substituted p-phenylenediamine compound, wherein the asymmetric diaryl-substituted p-phenylenediamine compound has the structure shown in the following formula A:
  • each R a is independently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5, each R b is independently selected from hydrogen and C1-C6 alkyl, and n is selected from 0-5 Integer; compounds of formula A do not include compounds in which (R a ) m substituted phenyl and (R b ) n substituted phenyl are the same;
  • the method includes:
  • each R a is independently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5; in the compound of formula D, each R b is independently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0 to 5; the compound of formula B is not the same as the compound of formula D.
  • the supported FeCl 3 catalyst is a catalyst obtained by supporting FeCl 3 on a carrier.
  • step (1) the reaction of step (1) is carried out in a non-polar solvent.
  • the reaction temperature of step (1) is 200-240°C.
  • the molar ratio of FeCl 3 contained in the supported FeCl 3 catalyst added in step (1) to hydroquinone added in step (1) is (0.08-0.4):1.
  • the molar ratio of the compound of formula B added in step (1) to the hydroquinone added in step (1) is (0.8-1.2):1.
  • reaction of step (1) is carried out in an inert gas atmosphere.
  • reaction of step (2) is carried out in a non-polar solvent.
  • the reaction temperature of step (2) is 230-270°C.
  • the molar ratio of the anhydrous FeCl 3 added in step (2) to the hydroquinone added in step (1) is (0.1-0.5):1.
  • the molar ratio of the compound of formula D added in step (2) to the hydroquinone added in step (1) is (1.0-1.8):1.
  • reaction of step (2) is carried out in an inert gas atmosphere.
  • the carrier of the supported FeCl 3 catalyst is selected from the group consisting of hydrogen-type molecular sieves, activated silica and activated alumina.
  • the mass ratio of FeCl 3 to the carrier is 1:(5-10).
  • the reaction of step (1) is performed in toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or in trimethylcyclohexane.
  • the reaction temperature of step (1) is 220-230°C.
  • the molar ratio of FeCl 3 contained in the supported FeCl 3 catalyst added in step (1) to hydroquinone added in step (1) is (0.1-0.25):1.
  • the molar ratio of the compound of formula B added in step (1) to the hydroquinone added in step (1) is (0.9-1.1):1.
  • step (1) the reaction of step (1) is carried out in a nitrogen atmosphere.
  • the reaction of step (2) is performed in toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or in trimethylcyclohexane.
  • the reaction temperature of step (2) is 240-260°C.
  • the molar ratio of the anhydrous FeCl 3 added in step (2) to the hydroquinone added in step (1) is (0.2-0.3):1.
  • the molar ratio of the compound of formula D added in step (2) to the hydroquinone added in step (1) is (1.2-1.5):1.
  • step (2) the reaction of step (2) is carried out in a nitrogen atmosphere.
  • the carrier of the supported FeCl catalyst is selected from hydrogen molecular sieves, activated silica and activated alumina; in the supported FeCl catalyst, the mass ratio of FeCl to the carrier is 1 : (5-10); the reaction of step (1) is in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylbenzene
  • the molar ratio of FeCl 3 contained in the supported FeCl 3 catalyst to hydroquinone is (0.1 -0.25): 1, the molar ratio of the compound of formula B to hydroquinone is (0.9-1.1): 1; the reaction of step (1) is carried out in a nitrogen atmosphere; the reaction of step (2) is carried out in toluene, xylene, Trimethylbenzene, chlorobenzene, dichlorobenzene,
  • the present invention also provides a method for preparing the compound of the following formula I:
  • R 1 and R 3 are each independently hydrogen or C1-C6 alkyl;
  • R 2 is C1-C6 alkyl; the compound of formula I does not include R 1 , R 2 substituted phenyl and R 3 substituted phenyl the same compound;
  • the method includes:
  • R 1 and R 2 are independently hydrogen or C1-C6 alkyl; in the compound of formula IV, R 3 is a C1-C6 alkyl; the compound of formula II and the compound of formula IV are different; or
  • the method includes:
  • R 1 and R 2 are independently hydrogen or C1-C6 alkyl; in the compound of formula IV, R 3 is a C1-C6 alkyl; the compound of formula II and the compound of formula IV are different.
  • the supported FeCl 3 catalyst is a catalyst obtained by loading FeCl 3 on a carrier.
  • the reaction of step (1) is carried out in a non-polar solvent.
  • the reaction temperature of step (1) is 200-240°C.
  • the molar ratio of FeCl3 contained in the supported FeCl3 catalyst added in step ( 1 ) to the hydroquinone added in step ( 1 ) is ( 0.08-0.4):1.
  • the molar ratio of the compound of formula II or compound of formula IV added in step (1) to the hydroquinone added in step (1) is (0.8-1.2 ): 1.
  • the reaction of step (1) is carried out under an inert gas atmosphere.
  • the reaction of step (2) is carried out in a non-polar solvent.
  • the reaction temperature of step (2) is 230-270°C.
  • the molar ratio of the anhydrous FeCl3 added in step ( 2 ) to the hydroquinone added in step (1) is (0.1-0.5):1 .
  • the molar ratio of the compound of formula IV or the compound of formula II added in step (2) to the hydroquinone added in step (1) is (1.0- 1.8): 1.
  • step (2) is carried out under an inert gas atmosphere.
  • the support of the supported FeCl3 catalyst is selected from the group consisting of hydrogen-type molecular sieves, activated silica, and activated alumina.
  • the mass ratio of FeCl 3 to the support is 1:(5-10).
  • the reaction of step (1) is performed in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylbenzene cyclohexane and/or trimethylcyclohexane.
  • the reaction temperature of step (1) is 220-230°C.
  • the molar ratio of FeCl3 contained in the supported FeCl3 catalyst added in step ( 1 ) to the hydroquinone added in step ( 1 ) is ( 0.1-0.25):1.
  • the molar ratio of the compound of formula II or compound of formula IV added in step (1) to the hydroquinone added in step (1) is (0.9-1.1 ): 1.
  • the reaction of step (1) is carried out under a nitrogen atmosphere.
  • the reaction of step (2) is performed in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylbenzene cyclohexane and/or trimethylcyclohexane.
  • the reaction temperature of step (2) is 240-260°C.
  • the molar ratio of the anhydrous FeCl3 added in step ( 2 ) to the hydroquinone added in step (1) is (0.2-0.3):1 .
  • the molar ratio of the compound of formula IV or the compound of formula II added in step (2) to the hydroquinone added in step (1) is (1.2-1.5 ): 1.
  • the reaction of step (2) is carried out under a nitrogen atmosphere.
  • the carrier of the supported FeCl3 catalyst is selected from hydrogen molecular sieves, activated silica and activated alumina; in the supported FeCl3 catalyst, the FeCl3 and the carrier are The mass ratio is 1: (5-10); the reaction of step (1) is in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and / or in trimethylcyclohexane; the reaction temperature of step (1) is 220-230 ° C; in the reaction system of step (1), the molar ratio of FeCl3 contained in the supported FeCl3 catalyst to hydroquinone is (0.1-0.25): 1, the molar ratio of the compound of formula II or the compound of formula IV to hydroquinone is (0.9-1.1): 1; the reaction of step (1) is carried out in a nitrogen atmosphere; the
  • R 1 is hydrogen, and R 2 and R 3 are each independently C1-C6 alkyl; or R 3 is hydrogen, and R 1 and R 2 Each independently is a C1-C6 alkyl group; or R 1 , R 2 and R 3 are each independently a C1-C6 alkyl group.
  • the C1-C6 alkyl group is selected from the group consisting of methyl, ethyl, propyl and butyl.
  • the C1-C6 alkyl group is selected from methyl and isobutyl.
  • the compound of formula I is selected from:
  • the present invention also provides a supported FeCl 3 catalyst, the carrier of the supported FeCl 3 catalyst is selected from hydrogen type molecular sieves, activated silica and activated alumina, and in the supported FeCl 3 catalyst, the FeCl 3 and the carrier are The mass ratio is 1:(5-10).
  • the carrier of the supported FeCl 3 catalyst is prepared by heating reaction between anhydrous FeCl 3 and the carrier in an alcohol solvent.
  • the ratio refers to the mass ratio
  • the percentage refers to the mass percentage
  • the terms “comprising”, “including” or “comprising” mean that the various ingredients are applicable together in the mixture or composition of the present invention.
  • the terms “consisting essentially of” and “consisting of” are encompassed by the terms “comprising”, “including” or “comprising”.
  • alkyl refers to a linear or branched monovalent saturated hydrocarbon group, usually containing 1-16 carbon atoms (C1-C16 alkyl), for example, containing 3-16 carbon atoms (C3-C16 alkyl).
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 1,4-dimethylpentyl, and t-octyl.
  • the asymmetric diaryl-substituted p-phenylenediamine compound refers to a compound that can be regarded as a compound obtained by substituting two different aryl groups for hydrogen atoms on two amino groups of p-phenylenediamine, respectively.
  • an asymmetric diaryl-substituted p-phenylenediamine compound can have the structure shown in the following formula A:
  • each R a is independently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5, each R b is independently selected from hydrogen and C1-C6 alkyl, and n is selected from 0-5 Integer; and (R a ) m substituted phenyl and (R b ) n substituted phenyl are not the same.
  • the same substituted phenyl group means that the number of substituents on the phenyl group, the position of each substituent and the substituent groups on the corresponding positions are all the same.
  • C1-C6 alkyl groups as R a or R b include but are not limited to methyl, ethyl, propyl and butyl, wherein propyl includes n-propyl and isopropyl, and butyl includes n-butyl , isobutyl, and tert-butyl, ie, each of Ra and Rb can each be independently selected from hydrogen, methyl, ethyl, propyl, and butyl.
  • the C1-C6 alkyl group as Ra or Rb is methyl or tert-butyl, ie, each of Ra and Rb is independently selected from hydrogen, methyl, and tert-butyl.
  • m is preferably an integer selected from 0-3, more preferably an integer selected from 0-2.
  • n is preferably an integer selected from 0-3, and more preferably an integer selected from 0-2.
  • the inventors of the present invention found that the asymmetric diaryl-substituted p-phenylenediamine compound (referred to as compound I or compound of formula I) as shown in the following formula I can not only provide long-term effects similar to antioxidant H or antioxidant 3100 Anti-aging properties and can improve bloomability:
  • R 1 and R 3 are each independently hydrogen or C1-C6 alkyl; R 2 is C1-C6 alkyl; and the phenyl substituted by R 1 and R 2 is different from the phenyl substituted by R 3 .
  • C1-C6 alkyl as R 1 , R 2 or R 3 includes but is not limited to methyl, ethyl, propyl and butyl, wherein propyl includes n-propyl and isopropyl, and butyl Included are n-butyl, isobutyl and tert - butyl, ie each R1, R2 and R3 can each be independently selected from hydrogen , methyl, ethyl, propyl and butyl.
  • the C1-C6 alkyl as R 1 , R 2 or R 3 is methyl or tert-butyl, ie each R 1 , R 2 and R 3 are each independently selected from hydrogen, methyl and tert-butyl base.
  • R 1 when R 1 is hydrogen, R 2 and R 3 represent different groups, or R 2 and R 3 represent the same groups but on respective substituted phenyl groups location is not the same.
  • R 1 when R 1 is hydrogen, R 2 and R 3 represent different groups.
  • R 1 and R 3 are not both hydrogen.
  • R 1 is hydrogen
  • R 2 and R 3 are each independently a C1-C6 alkyl group
  • R 2 and R 3 are different.
  • R 3 is hydrogen, and R 1 and R 2 are each independently C1-C6 alkyl.
  • R 1 , R 2 , and R 3 are each independently C1-C6 alkyl.
  • Compound 1 has the structure shown in any one of Formulas 1-1 to 1-6 below:
  • the present invention provides a method for an asymmetric diaryl-substituted p-phenylenediamine compound (referred to as a compound of formula A) having the structure shown in the following formula A:
  • each R a is independently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5, each R b is independently selected from hydrogen and C1-C6 alkyl, and n is selected from 0-5 Integer; compounds of formula A do not include compounds in which (R a ) m substituted phenyl and (R b ) n substituted phenyl are the same;
  • the method includes the following steps:
  • each R a is independently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5; in the compound of formula D, each R b is independently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0 to 5; the compound of formula B is not the same as the compound of formula D.
  • the preferred R a , the preferred m in the compound B, the preferred R b , and the preferred n in the compound D can be as described in any of the embodiments herein.
  • the method of preparing the compound of formula I may comprise the following steps:
  • R 1 and R 2 are independently hydrogen or C1-C6 alkyl; in the compound of formula IV, R 3 is a C1-C6 alkyl; the compound of formula II and the compound of formula IV are different.
  • the method of preparing the compound of formula I may also comprise the steps of:
  • R 1 and R 2 are independently hydrogen or C1-C6 alkyl; in the compound of formula IV, R 3 is a C1-C6 alkyl; the compound of formula II and the compound of formula IV are different.
  • the preferred R 1 and R 2 in compound II and the preferred R 3 in compound IV can be as described in any of the embodiments herein.
  • the present invention adopts a two-step method to prepare asymmetric diaryl-substituted p-phenylenediamine.
  • supported FeCl 3 is used as a catalyst. Since ferric iron is stably bonded to the surface of the carrier, its catalytic activity is weaker than that of free FeCl 3 . Therefore, the target product arylaminophenol is restricted from further reacting with aromatic amines to generate symmetrical diaryl-p-phenylenediamine; in addition, the pore structure of the carrier further limits the generation of diaryl-p-phenylenediamine from space.
  • the reaction of step (1) is carried out in a non-polar solvent; for example, the non-polar solvent can be toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane Hexane, trimethylcyclohexane, etc., preferably toluene or xylene.
  • the reaction of step (1) is carried out under the conditions of raising the temperature to reflux for azeotropy and dehydration.
  • the reaction temperature of the step (1) is preferably 200 to 240°C, more preferably 220 to 230°C.
  • the way of dehydration can be conventional in the art, for example, dehydration can be done by using a water separator.
  • the reaction of step (1) is preferably carried out in an inert gas (eg nitrogen) atmosphere.
  • the supported FeCl 3 catalyst refers to a catalyst obtained by supporting FeCl 3 on a carrier.
  • ferric iron is stably bonded to the carrier, and the mass ratio of FeCl 3 to the carrier is preferably 1:(5-10).
  • the carrier of the supported FeCl 3 catalyst can be hydrogen molecular sieve, activated silica or activated alumina.
  • activated alumina and activated silica refer to solid silica and solid alumina that contain hydroxyl groups on the inner and outer surfaces and are porous.
  • the hydrogen type molecular sieve can be, for example, GENERAL-REAGENT, 4A of Shanghai Titan Chemical Co., Ltd.
  • the active silica can be, for example, GENERAL-REAGENT, G72651A from Shanghai Titan Chemical Co., Ltd.
  • the activated alumina can be, for example, GENERAL-REAGENT, G21116K from Shanghai Titan Chemical Co., Ltd.
  • the supported FeCl 3 catalyst used in the present invention can be prepared by heating reaction between anhydrous FeCl 3 and a carrier in a solvent.
  • the solvent used in preparing the supported FeCl 3 catalyst can be an alcohol solvent, preferably a C1-C3 monohydric alcohol, such as methanol.
  • the mass ratio of FeCl 3 and solvent in the reaction system is usually 1:5 to 1:20, for example, 1:9 to 1:19.
  • the mass ratio of FeCl 3 and carrier in the reaction system is usually 1:(5-10).
  • the reaction is usually carried out under stirring and refluxing conditions.
  • the reaction time is usually 5 to 10 hours, preferably 7 to 8 hours.
  • the solvent is removed to obtain a supported FeCl 3 catalyst.
  • the method of removing the solvent can be, for example, distilling off the solvent under heating and vacuum conditions.
  • the supported FeCl catalyst is prepared by the following method:
  • anhydrous FeCl 3 prepares a solution with a concentration of 5-10 wt % with methanol, add it into a four-necked flask equipped with mechanical stirring, a thermometer and a reflux condenser, add a certain amount of dried carrier, FeCl 3 and FeCl 3
  • the mass ratio of the carrier is 1:(5 ⁇ 10), start the mechanical stirring, gradually heat up to methanol reflux, keep refluxing for 7 ⁇ 8h, then steam out methanol, heat up to 140 ⁇ 150°C and vacuum to about 10kPa absolute pressure, keep 5 ⁇ 6h, after cooling, quickly pour it into a clean and dry reagent bottle, and store it in a desiccator.
  • the molar ratio of FeCl 3 contained in the added supported FeCl 3 catalyst to the added hydroquinone is preferably (0.08-0.4):1, more preferably (0.1-0.25):1.
  • the molar ratio of the added compound of formula B (for example, the compound of formula II or the compound of formula IV) to the added hydroquinone is preferably (0.8-1.2): 1, more preferably (0.9-1.1): 1.
  • Whether the reaction in step (1) is completed can be determined by detecting whether water is generated, and the reaction is completed when no more water is generated.
  • the catalyst is filtered out while hot, and the solvent and unreacted compound of formula B (for example, compound of formula II or compound of formula IV) are distilled off under reduced pressure to obtain compound of formula C (for example, compound of formula III or compound of formula III) ' compound); filtration and vacuum distillation are preferably carried out at the reaction temperature of step (1); the vacuum degree of vacuum distillation is preferably lower than 5 mmHg.
  • the reaction of step (2) is carried out in a non-polar solvent; for example, the non-polar solvent can be toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane Hexane, trimethylcyclohexane, etc., preferably toluene or xylene.
  • the reaction of step (2) is carried out under the conditions of raising the temperature to reflux for azeotropy and dehydration.
  • the reaction temperature of step (2) is preferably 230-270°C, preferably 240-260°C.
  • the way of dehydration can be conventional in the art, for example, dehydration can be done by using a water separator.
  • the reaction of step (2) is preferably carried out in an inert gas (eg nitrogen) atmosphere.
  • the molar ratio of the anhydrous FeCl 3 added in step (2) to the hydroquinone added in step (1) is preferably (0.1-0.5):1, more preferably (0.2-0.3):1.
  • the molar ratio of the compound of formula D (for example, the compound of formula IV or the compound of formula II) added in step (2) to the hydroquinone added in step (1) is preferably (1.0-1.8): 1, more preferably (1.2 -1.5): 1.
  • Whether the reaction in step (2) is completed can be determined by detecting whether water is generated, and the reaction is completed when no more water is generated.
  • the temperature is lowered to about 80 ⁇ 100° C., an appropriate amount of lye is added to neutralize, the temperature is increased and the pressure is reduced to distill out water, solvent and unreacted compound of formula D (for example, compound of formula IV or compound of formula II), Filter while hot, and the filtrate is cooled and solidified to obtain a compound of formula A (for example, a compound of formula I);
  • the neutralization time is preferably 0.5-1.5h;
  • the lye can be, for example, an aqueous solution of a weakly basic salt;
  • the weakly basic salt can be sodium carbonate, Potassium carbonate, sodium phosphate, potassium phosphate, etc.;
  • the vacuum degree of vacuum distillation is preferably lower than 5mmHg;
  • the temperature of vacuum distillation is preferably 250-300°C;
  • the temperature of filtration is preferably 130-160
  • the method of the present invention can prepare a single-component asymmetric diaryl-substituted p-phenylenediamine compound, and the prior art is difficult to prepare a single-component asymmetric diaryl-p-phenylenediamine;
  • reaction conditions are not harsh: the reaction can be carried out under the catalysis of heating and supported FeCl 3 catalyst or anhydrous FeCl 3 .
  • Compound I of the present invention can be used as a rubber antioxidant, providing longer lasting protection than conventional antioxidants without blooming. Accordingly, the present invention provides rubber compositions containing one or more of the compounds I of the present invention.
  • Raw materials for rubber compositions generally include diene elastomers, reinforcing fillers, antioxidants, and cross-linking agents.
  • the amount of diene elastomer, reinforcing filler, anti-aging agent and cross-linking agent may be the conventional amount in the art. Based on 100 parts by mass of diene elastomer, the amount of Compound I in the rubber composition may be 0.1-5 parts by mass, for example, 0.5-5 parts by mass, 1-3 parts by mass, and 1-2 parts by mass.
  • the rubber composition includes unvulcanized rubber and vulcanized rubber. Vulcanized rubber can be obtained by vulcanizing (curing) the unvulcanized rubber.
  • Diene elastomers refer to elastomers whose monomers comprise a diene (eg, butadiene, isoprene). Diene elastomers suitable for use in the present invention may be various diene elastomers known in the art, including but not limited to those selected from natural rubber (NR), cis-butadiene rubber (BR), isoprene rubber, styrene-butadiene rubber ( SBR), neoprene (CR), nitrile rubber (NBR), isoprene/butadiene copolymers, isoprene/styrene copolymers and isoprene/butadiene/styrene copolymers one or more of these.
  • NR natural rubber
  • BR cis-butadiene rubber
  • SBR styrene-butadiene rubber
  • SBR styrene-butadiene rubber
  • CR neo
  • the diene elastomer is composed of natural rubber (such as SCR5) and cis-butadiene rubber (such as BR9000); the mass ratio of natural rubber and cis-butadiene rubber is not particularly limited, for example, 1:9 to 9:1, 2:8 to 8:2, 3:7 to 7:3, 4:6 to 6:4, or about 1:1.
  • the reinforcing filler may be one conventionally used in rubber, including but not limited to one or more selected from the group consisting of carbon black, titanium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, clay, and talc kind.
  • the amount of the reinforcing filler may be 40-60 parts by mass per 100 parts by mass of the diene elastomer.
  • the crosslinking agent can be sulfur.
  • the cross-linking agent may be used in an amount of 1-3 parts by mass per 100 parts by mass of the diene elastomer.
  • the amount of the antioxidant may be 0.1-5 parts by mass, 0.5-5 parts by mass, 1-3 parts by mass or 1-2 parts by mass of the antioxidant per 100 parts by mass of the diene elastomer.
  • the anti-aging agent may be Compound I or a combination of Compound I and a conventional anti-aging agent.
  • the raw materials of the rubber composition may also include other components commonly used in rubber, including but not limited to auxiliary agents and accelerators.
  • the amount of adjuvant and accelerator can be the conventional amount in the art.
  • Adjuvants may include softeners used to improve processability.
  • the softener can be a petroleum-based softener such as aromatic oil, processing oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petrolatum, etc., or a fatty oil-based softener such as castor oil, linseed oil, rapeseed oil, coconut Oils, waxes (such as beeswax, carnauba wax and lanolin), tall oil, linoleic acid, palmitic acid, stearic acid and lauric acid, etc.
  • Auxiliaries can also include active agents, such as zinc oxide, which can accelerate the vulcanization speed, improve the thermal conductivity, wear resistance, tear resistance and the like of the rubber.
  • a total of 5-20 parts by mass of adjuvants is used per 100 parts by mass of diene elastomer, for example, 2-8 parts by mass of aromatic oil, 2-8 parts by mass of zinc oxide and 1-4 parts by mass of hardener can be used fatty acid.
  • Accelerators are usually vulcanization accelerators, which can be sulfonamides, thiazoles, thiurams, thioureas, guanidines, dithiocarbamates, aldehyde amines, aldehyde ammonia, imidazoline and xanthogen At least one of acid-based vulcanization accelerators.
  • the accelerator may be the accelerator NS (N-tert-butyl-2-benzothiazole sulfenamide). Typically, 0.5-1.5 parts by mass of the accelerator is used per 100 parts by mass of the diene elastomer.
  • plasticizers such as DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate) can also be used in the rubber composition , DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (o- butyl benzyl phthalate), DWP (dilauryl phthalate) and DCHP (dicyclohexyl phthalate) and the like.
  • the amount of the plasticizer is the conventional amount in the art.
  • the unvulcanized rubber of the present invention can be prepared by a conventional rubber mixing method, for example, a two-stage mixing method is used to prepare: one-stage internal mixer mixing, mixing diene elastomer, reinforcing filler, auxiliary agent and anti-aging agent, and degumming
  • a two-stage mixing method is used to prepare: one-stage internal mixer mixing, mixing diene elastomer, reinforcing filler, auxiliary agent and anti-aging agent, and degumming
  • the temperature is above 110 °C; the two-stage open mill is mixed, and the glue obtained in the first stage is mixed with the cross-linking agent and accelerator.
  • the diene elastomer is first added to a thermomechanical mixer (such as an internal mixer), and after kneading for a certain period of time, the reinforcing filler, auxiliary agent, and anti-aging agent are added, and the kneading is continued until the mixing is uniform, and the reinforcing filler, auxiliary agent, and anti-aging agent are added.
  • a thermomechanical mixer such as an internal mixer
  • the temperature during kneading is controlled between 110°C and 190°C, preferably between 150°C and 160°C; then, the mixture is cooled to below 100°C, crosslinking agent and accelerator are added, kneaded again, and kneaded During the period, the temperature is controlled below 110°C, such as about 70°C, to obtain unvulcanized rubber.
  • the unvulcanized rubber of the present invention can be vulcanized by a conventional vulcanization method to obtain a vulcanized rubber;
  • the vulcanization temperature is usually 130 °C-200 °C, such as about 145 °C;
  • the vulcanization time depends on the vulcanization temperature, vulcanization system and vulcanization kinetics, usually 15 -60 minutes, like 30 minutes or so.
  • the unvulcanized rubber obtained by kneading can be subjected to conventional tableting prior to vulcanization.
  • the present invention also provides a rubber product having the rubber composition of the present invention as its rubber component.
  • Rubber products can be tires, rubber shoes, weather strips, sound insulation boards, shock pads, etc.
  • the rubber article is a tire, such as a tire tread, belt, and sidewall.
  • the belt layer of the tire in addition to the rubber composition of the present invention, may also contain reinforcing materials conventionally used in the art.
  • the asymmetric diaryl-substituted p-phenylenediamine compound of the present invention can prevent the rubber product from blooming during use.
  • the present invention also provides the use of the compound I of the present invention for improving the anti-aging properties and/or blooming properties of rubber or rubber products.
  • Example 1-11 the supported FeCl catalyst prepared by using hydrogen-type molecular sieve (Shanghai Titan Chemical Co., Ltd., GENERAL-REAGENT, 4A) as a carrier, and active silica (Shanghai Titan Chemical Co., Ltd. ) was used in Example 12.
  • GENERAL-REAGENT, G72651A the supported FeCl catalyst prepared by the carrier
  • Example 13 the supported FeCl catalyst prepared by using activated alumina (Shanghai Titan Chemical Co., Ltd., GENERAL-REAGENT, G21116K) as the carrier .
  • Test Examples 1-4 were prepared according to the formula shown in Table 2, which specifically included the following steps:
  • the obtained rubber composition is calendered into a sheet shape (with a thickness of 2-3 mm), and then vulcanized.
  • the vulcanization temperature is 145° C. and the time is 30 minutes.
  • N550 Cabot Corporation, carbon black N550;
  • Aromatic oil Shanghai Titan Technology Co., Ltd., general reagent;
  • Stearic acid Shanghai Titan Technology Co., Ltd., general reagent, stearic acid (AR);
  • Zinc oxide Shanghai Titan Technology Co., Ltd., general reagent, zinc oxide (AR);
  • NS Sennics Technology Co., Ltd., vulcanization accelerator NS;
  • Antioxidant H Sennics Technology Co., Ltd.
  • Anti-aging agent 3100 India Acmechem Limited (Acmechem Limited, India);
  • Test Example 1 Test case 2 Test case 3 Test Example 4 SCR5 50.0 50.0 50.0 50.0 BR 50.0 50.0 50.0 50.0 N550 50.0 50.0 50.0 50.0 Aromatic oil 5.0 5.0 5.0 5.0 5.0 Zinc oxide 5.0 5.0 5.0 5.0 5.0 Stearic acid 2.0 2.0 2.0 Anti-aging agent H 1.5 Compound I-1 1.5 Anti-aging agent 3100 1.5 Compound I-6 1.5 NS 0.8 0.8 0.8 S 1.5 1.5 1.5 1.5 1.5 1.5 total 165.8 165.8 165.8 165.8 165.8 165.8
  • Test pieces of various rubber compositions were subjected to an ozone deterioration test under the conditions of a temperature of 40° C., an ozone concentration of 50 pphm, and an elongation of 20%.
  • the time to appearance of cracks of grades 1c to 4c was recorded. The longer the time to form cracks of the same grade, the better the resistance to ozone aging.
  • the experimental results are shown in Table 3.
  • the numbers in "1c ⁇ 4c" represent the crack width grade, and the letters represent the crack number grade; 1 means the crack width is greater than 0mm and less than 0.1mm, 2 means the crack width is greater than or equal to 0.1mm and less than 0.2mm, 3 means the crack The width is greater than or equal to 0.2mm and less than 0.4mm, 4 means the crack width is greater than or equal to 0.4mm; c means the number of cracks per centimeter is greater than or equal to 40.
  • Test Example 1 Test case 2 Test case 3 Test Example 4 Class 1c crack 3h 3h 3h 3h
  • Test Example 1 Test case 2 Test case 3 Test Example 4 1 week Obvious frosting phenomenon The surface has not changed Slight frosting phenomenon The surface has not changed Two weeks Large area hoarfrost The surface has not changed Large area hoarfrost The surface has not changed

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de préparation pour un composé p-phénylènediamine substitué par un groupe diaryle asymétrique. Le composé présente la structure telle que présentée dans la formule suivante (A). Le procédé comprend : (1) la mise en réaction de p-dihydroxybenzène avec un composé de formule (B) en présence d'un catalyseur FeCl3 supporté, pour obtenir un composé de formule (C) ; et (2) la mise en réaction du composé de formule (C) avec un composé de formule (D) en présence d'un catalyseur FeCl3 anhydre, pour obtenir un composé de formule (A). Dans les formules (A) à (D), les groupes sont définis tels que décrits dans le texte. Le procédé permet de préparer de manière efficace et pratique le composé p-phénylènediamine substitué par un groupe diaryle asymétrique.
PCT/CN2021/115983 2020-09-01 2021-09-01 Procédé de préparation pour composé p-phénylènediamine substitué par un groupe diaryle asymétrique WO2022048565A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010904961.0 2020-09-01
CN202010904961.0A CN114105779A (zh) 2020-09-01 2020-09-01 不对称二芳基取代型对苯二胺类化合物的制备方法

Publications (1)

Publication Number Publication Date
WO2022048565A1 true WO2022048565A1 (fr) 2022-03-10

Family

ID=80360375

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/115983 WO2022048565A1 (fr) 2020-09-01 2021-09-01 Procédé de préparation pour composé p-phénylènediamine substitué par un groupe diaryle asymétrique

Country Status (2)

Country Link
CN (1) CN114105779A (fr)
WO (1) WO2022048565A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181025A (zh) * 2022-07-01 2022-10-14 山东阳谷华泰化工股份有限公司 N-苯基-n’-（对烷基苯基）对苯二胺及其制备方法和应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326080A (en) * 1979-07-03 1982-04-20 Bayer Aktiengesellschaft Process for the preparation of 4-amino-diphenylamines
US5750786A (en) * 1997-02-20 1998-05-12 The Goodyear Tire & Rubber Company Process for the preparation of unsubstituted and substituted diaryl phenylenediamines
CN1611486A (zh) * 2003-10-29 2005-05-04 龙口科达化工有限公司 精细化工中间体对羟基二苯胺及其制备工艺
CN101703936A (zh) * 2009-11-30 2010-05-12 上海交通大学 磁性纳米催化剂及其制备方法
CN106608827A (zh) * 2015-10-21 2017-05-03 江苏圣奥化学科技有限公司 芳基取代对苯二胺类物质的制备方法
CN105727957B (zh) * 2014-12-09 2019-04-30 中国科学院大连化学物理研究所 一种负载型铁镍磷化物催化剂材料及其应用
CN106000404B (zh) * 2016-05-24 2019-06-21 江南大学 一种用于费托合成的碳改性二氧化硅载体负载的铁基催化剂的制备及其应用
CN110734380A (zh) * 2018-07-18 2020-01-31 圣奥化学科技有限公司 一种二芳基对苯二胺类防老剂的制备方法
CN111153871A (zh) * 2020-01-19 2020-05-15 江苏方圆芳纶研究院有限公司 取代苯胺基-苯并噻唑-2-硫酮类化合物及其制备方法和应用
WO2020248572A1 (fr) * 2019-06-14 2020-12-17 Sennics Co., Ltd. Composé antidégradant à faible pollution et composition d'antidégradant et composition de caoutchouc le comprenant pour pneus

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326080A (en) * 1979-07-03 1982-04-20 Bayer Aktiengesellschaft Process for the preparation of 4-amino-diphenylamines
US5750786A (en) * 1997-02-20 1998-05-12 The Goodyear Tire & Rubber Company Process for the preparation of unsubstituted and substituted diaryl phenylenediamines
CN1611486A (zh) * 2003-10-29 2005-05-04 龙口科达化工有限公司 精细化工中间体对羟基二苯胺及其制备工艺
CN101703936A (zh) * 2009-11-30 2010-05-12 上海交通大学 磁性纳米催化剂及其制备方法
CN105727957B (zh) * 2014-12-09 2019-04-30 中国科学院大连化学物理研究所 一种负载型铁镍磷化物催化剂材料及其应用
CN106608827A (zh) * 2015-10-21 2017-05-03 江苏圣奥化学科技有限公司 芳基取代对苯二胺类物质的制备方法
CN106000404B (zh) * 2016-05-24 2019-06-21 江南大学 一种用于费托合成的碳改性二氧化硅载体负载的铁基催化剂的制备及其应用
CN110734380A (zh) * 2018-07-18 2020-01-31 圣奥化学科技有限公司 一种二芳基对苯二胺类防老剂的制备方法
WO2020248572A1 (fr) * 2019-06-14 2020-12-17 Sennics Co., Ltd. Composé antidégradant à faible pollution et composition d'antidégradant et composition de caoutchouc le comprenant pour pneus
CN111153871A (zh) * 2020-01-19 2020-05-15 江苏方圆芳纶研究院有限公司 取代苯胺基-苯并噻唑-2-硫酮类化合物及其制备方法和应用

Also Published As

Publication number Publication date
CN114105779A (zh) 2022-03-01

Similar Documents

Publication Publication Date Title
CN106459502B (zh) 橡胶组合物、轮胎、双苯胺基化合物和抗老化剂
TW200831521A (en) Mercaptofunctional silane and process for its preparation
EP3805306B1 (fr) Composition de caoutchouc et pneu
WO2022048565A1 (fr) Procédé de préparation pour composé p-phénylènediamine substitué par un groupe diaryle asymétrique
WO2018025966A1 (fr) Composition de caoutchouc, pneu, additif et composé hydrazide
US6329551B1 (en) Phenylenediamine derivative, production method thereof and antioxidant for rubber using it as effective constituent
JP2010536952A (ja) ゴム組成物
JP7162082B2 (ja) 新規な長時間作用型ゴム老化防止剤およびそれを含むタイヤ用ゴム組成物
WO2022041528A1 (fr) Nouveau composé p-phénylènediamine, son procédé de préparation et son application
JP7257973B2 (ja) ゴム組成物及びタイヤ
JP7271445B2 (ja) ゴム組成物及びタイヤ
CN116554038B (zh) 多烷基对苯二胺类防老剂、其中间体及制备方法
WO2024098461A1 (fr) Agent anti-vieillissement à base de polyalkyl p-phénylènediamine, intermédiaire de celui-ci et procédé de préparation s'y rapportant
WO2024098460A1 (fr) Agent anti-vieillissement de caoutchouc et son procédé de préparation
WO2021088721A1 (fr) Composé ayant des effets anti-vieillissement et de résistance à la décoloration et son procédé de préparation
US20020128499A1 (en) 2-Thio-5-amino substituted benzoquinones, their manufacture and their use in rubber
CN116589369A (zh) 一种橡胶防老剂及其制备方法
JP3757581B2 (ja) フェニレンジアミン誘導体の製造法
JP2012214437A (ja) ２，２，４−トリメチル−１，２−ジヒドロキノリンのオリゴマー含有組成物の製造方法
SK281439B6 (sk) Prostriedok na báze vyššiemolekulových, kruhovosubstituovaných n,n'-difenyl-p-fenyléndiamínov, spôsob jeho prípravy a polymérna kompozícia s jeho obsahom
EP0409565A1 (fr) Composition de caoutchouc pour pneumatiques
JP2012197418A (ja) 加硫ゴムが有する耐熱性の改善方法
CN110691766A (zh) 制备具有抗降解剂和抗疲劳功效的化合物的方法
SK122295A3 (en) Mixture liquid stabilizer for rubbers, preparation method thereof and mixtures prepared with its use
JP2012214438A (ja) ２，２，４−トリメチル−１，２−ジヒドロキノリンのオリゴマー含有組成物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21863629

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21863629

Country of ref document: EP

Kind code of ref document: A1