WO2021088721A1 - 具有抗老化和耐变色功效的化合物及其制备方法 - Google Patents

具有抗老化和耐变色功效的化合物及其制备方法 Download PDF

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WO2021088721A1
WO2021088721A1 PCT/CN2020/125100 CN2020125100W WO2021088721A1 WO 2021088721 A1 WO2021088721 A1 WO 2021088721A1 CN 2020125100 W CN2020125100 W CN 2020125100W WO 2021088721 A1 WO2021088721 A1 WO 2021088721A1
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Prior art keywords
compound
reaction
rubber
phenylenediamine
cycloalkyl
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PCT/CN2020/125100
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English (en)
French (fr)
Inventor
郭湘云
邢金国
刘燕祥
李辉
高杨
唐志民
朱海波
祁琦
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圣奥化学科技有限公司
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Priority to CA3159789A priority Critical patent/CA3159789A1/en
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
Priority to BR112022007951A priority patent/BR112022007951A2/pt
Priority to IL292560A priority patent/IL292560A/en
Priority to MX2022005174A priority patent/MX2022005174A/es
Priority to JP2022525000A priority patent/JP2023501170A/ja
Priority to EP20884942.2A priority patent/EP4056561A4/en
Priority to KR1020227018541A priority patent/KR20220106984A/ko
Priority to AU2020378456A priority patent/AU2020378456A1/en
Priority to PE2022000714A priority patent/PE20230250A1/es
Publication of WO2021088721A1 publication Critical patent/WO2021088721A1/zh
Priority to ZA2022/04679A priority patent/ZA202204679B/en
Priority to US17/736,074 priority patent/US20220306590A1/en
Priority to CONC2022/0006895A priority patent/CO2022006895A2/es

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/70—Other substituted melamines
    • 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
    • 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
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • 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

Definitions

  • the invention belongs to the field of rubber additives, and specifically relates to a compound with anti-aging and discoloration resistance effects and a preparation method thereof.
  • rubber products especially tire products usually use p-phenylenediamine compounds as anti-aging agents.
  • dialkyl p-phenylenediamine, alkyl aryl p-phenylenediamine and diaryl p-phenylenediamine are widely used, including N-(1,3-dimethylbutyl)-N' -Phenyl-p-phenylenediamine (abbreviated as 6PPD or 4020), N-isopropyl-N'-phenyl-p-phenylenediamine (abbreviated as IPPD), N,N'-bis(1,4-dimethylpentyl) ) P-phenylenediamine (abbreviated as 77PD), diphenyl-p-phenylenediamine mixture (abbreviated as antioxidant 3100 or DTPD), etc.
  • 6PPD N-(1,3-dimethylbutyl)-N' -Phenyl-p-phenylenediamine
  • IPPD
  • the existing anti-aging agent products have a relatively significant effect in anti-aging in tires and other fields
  • the anti-aging agent in rubber products or tires will quickly migrate to the surface of rubber products or tires due to their discoloration during use. It can cause pollution, discoloration, damage, etc. on the surface of rubber products or tires; at the same time, because the anti-aging agent migrates to the surface of tires and other rubber products too fast, which leads to a rapid decrease in the content of anti-aging agents in the product, its long-lasting protection performance will be relatively compared difference.
  • the present invention provides a series of compounds with anti-aging and discoloration effects and preparation methods thereof.
  • the compound of the present invention has more long-lasting anti-aging performance, and has discoloration resistance. It can be used as an anti-aging agent in rubber products, especially rubber tires, and can prevent rubber products or rubber tires from being exposed to light, heat and oxygen during use. Deterioration caused by aging, fatigue, etc.
  • the present invention provides a compound represented by the following formula (I):
  • R is a C3-C16 alkyl group, a C3-C16 alkyl group substituted with a C3-C10 cycloalkyl group, a C3-C10 cycloalkyl group, or a C3-C10 cycloalkyl group substituted with a C3-C16 alkyl group;
  • R 1 and R 2 are the same or different, each independently selected from C3 ⁇ C10 alkyl, C3 ⁇ C10 cycloalkyl or C6 ⁇ C14 aryl substituted C3 ⁇ C10 alkyl, C3 ⁇ C10 cycloalkyl, C3 ⁇ C10 alkane C3-C10 cycloalkyl groups, C6-C14 aryl groups, and C6-C14 aryl groups substituted with C3-C10 alkyl groups.
  • R is C3-C10 alkyl or C3-C10 cycloalkyl, preferably C3-C10 branched alkyl or C3-C10 cycloalkyl, more preferably isopropyl, tert-butyl Group, tert-octyl or cyclohexyl.
  • R 1 and R 2 are the same or different, and are each independently a C3-C10 alkyl group or a phenyl group, preferably each independently a C3-C10 branched chain alkyl group or a phenyl group, more preferably each independently Isopropyl, 1,4-dimethylpentyl or phenyl.
  • the compound is selected from:
  • the present invention also provides a method for preparing the compound according to any embodiment of the present invention, comprising:
  • R, R 1 and R 2 in the compound of formula A, formula B and formula (I) are as defined in any embodiment of the present invention.
  • the basic solid powder is added in the reaction of step (1), and the reaction temperature is 0-35°C.
  • lye is added in the reaction of step (2), and the reaction temperature is 50-100°C.
  • the reaction temperature in step (3) is 80-180°C.
  • R 1 and R 2 are the same, and the steps (2) and (3) are combined into step (2'): Intermediate A and NR 1 -p-phenylenediamine are reacted to prepare The compound of formula (I) is obtained.
  • lye is added to the reaction in step (2'), and the reaction is first carried out at 50-100°C, and then at 80-180°C.
  • the present invention also provides a rubber composition containing the compound according to any one of the embodiments of the present invention.
  • the present invention also provides a rubber product prepared by using the rubber composition according to any embodiment of the present invention as a rubber component; preferably, the rubber product is a tire.
  • the present invention also provides the use of the compound according to any embodiment of the present invention to improve the anti-aging performance and/or discoloration resistance of rubber or rubber products; preferably, the rubber product is a tire.
  • alkyl refers to a linear or branched monovalent saturated hydrocarbon group, usually containing 1 to 16 carbon atoms (C1 to C16 alkyl), preferably 3 to 16 carbon atoms (C3 to C16 alkyl).
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1,4-dimethylpentyl, and tert-octyl.
  • the alkyl group may be optionally substituted by an aryl group or a cycloalkyl group, and the number of substituents is usually one.
  • substituted alkyl groups include, but are not limited to, cyclohexylmethyl, benzyl, and phenethyl.
  • alkylene refers to a straight or branched divalent saturated hydrocarbon group, usually containing 1 to 16 carbon atoms (C1 to C16 alkylene), preferably containing 3 to 16 carbon atoms (C3 to C16 alkylene) ).
  • alkylene include, but are not limited to, methylene, ethylene, and 1,3-propylene.
  • cycloalkyl refers to a monovalent saturated hydrocarbon ring containing 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms.
  • cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.
  • the cycloalkyl group may be optionally substituted by an alkyl group.
  • the number of substituents can be 1 or 2.
  • substituted cycloalkyl groups include, but are not limited to, methylcyclohexyl.
  • cycloalkylene refers to a divalent saturated hydrocarbon ring containing 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms.
  • Examples of cycloalkylene include, but are not limited to, 1,2-cyclopentadiyl and 1,2-cyclohexadiyl.
  • the aryl group refers to the monovalent group remaining after removing a hydrogen atom from the aromatic nucleus carbon of an aromatic hydrocarbon molecule.
  • the number of ring carbon atoms of the aryl group is usually 6-14.
  • Exemplary aryl groups include phenyl and naphthyl.
  • the aryl group may be optionally substituted with an alkyl group, a cycloalkyl group, and/or an aryl group.
  • the number of substituents is usually 1 or 2.
  • Examples of exemplary substituted aryl groups include, but are not limited to, 2-methylphenyl, 4-cyclohexylphenyl, 4-(2-methylcyclohexyl)phenyl, and 4-biphenyl.
  • the present invention finds that a compound having a structure as shown in formula (I) can provide better weather resistance, durability, and discoloration resistance than conventional antioxidants, and its specific structure is as follows:
  • R is a C3-C16 alkyl group, a C3-C16 alkyl group substituted with a C3-C10 cycloalkyl group, a C3-C10 cycloalkyl group, or a C3-C10 cycloalkyl group substituted with a C3-C16 alkyl group;
  • R 1 and R 2 are the same or different, each independently selected from C3 ⁇ C10 alkyl, C3 ⁇ C10 cycloalkyl or C6 ⁇ C14 aryl substituted C3 ⁇ C10 alkyl, C3 ⁇ C10 cycloalkyl, C3 ⁇ C10 alkane C3-C10 cycloalkyl groups, C6-C14 aryl groups, and C6-C14 aryl groups substituted with C3-C10 alkyl groups.
  • R is a C3-C10 alkyl group or a C3-C10 cycloalkyl group.
  • R is a C3-C10 alkyl group, preferably a C3-C10 branched chain alkyl group or a C3-C10 cycloalkyl group, such as isopropyl, t-butyl, t-octyl or cyclohexyl.
  • R 1 and R 2 are each independently a C3-C10 alkyl group or a phenyl group.
  • R 1 and R 2 are each independently a C3-C10 branched alkyl group or a phenyl group.
  • R 1 and R 2 are each independently isopropyl, 1,4-dimethylpentyl, or phenyl.
  • R is tert-butyl or tert-octyl
  • R 1 and R 2 are each independently 1,4-dimethylpentyl or phenyl.
  • the compound of the structure represented by formula (I) of the present invention can be prepared in three steps:
  • cyanuric chloride (TCT) and NH 2 R are used as raw materials to prepare intermediate A, where R is a C3-C16 alkyl group, a C3-C16 alkyl group substituted with a C3-C10 cycloalkyl group, and a C3 ⁇ C10 cycloalkyl or C3 ⁇ C10 cycloalkyl substituted with C3 ⁇ C16 alkyl;
  • intermediate A is reacted with NR 1 -p-phenylenediamine to prepare intermediate B, wherein R 1 is C3 ⁇ C10 alkyl, C3 ⁇ C10 cycloalkyl or C6 ⁇ C14 aryl substituted C3 ⁇ C10 alkyl, C3-C10 cycloalkyl, C3-C10 cycloalkyl substituted with C3-C10 alkyl, C6-C14 aryl or C6-C14 aryl substituted with C3-C10 alkyl;
  • intermediate B is reacted with NR 2 -p-phenylenediamine to prepare the target compound of formula (I), wherein R 2 is C3 ⁇ C10 alkyl, C3 ⁇ C10 cycloalkyl or C6 ⁇ C14 aryl. Substituted C3-C10 alkyl, C3-C10 cycloalkyl, C3-C10 cycloalkyl substituted with C3-C10 alkyl, C6-C14 aryl or C6-C14 aryl substituted with C3-C10 alkyl;
  • the preferred R, R 1 and R 2 in the intermediate A, the intermediate B and the compound of formula (I) can be as described in any of the embodiments herein.
  • an excess of NH 2 R can be used. Compared with cyanuric chloride, NH 2 R can generally exceed an excess of 10% or less. In certain embodiments, the NH 2 R excess is 8% or less or 5% or less.
  • an excessive amount of a substance means that the added amount of the substance is greater than the added amount of cyanuric chloride.
  • the percentage value of excess is based on the amount of the substance. For example, when 1 mol of cyanuric chloride is used, an excess of 10% or less of NH 2 R means that 1 mol to 1.1 mol of NH 2 R can be used.
  • the first step of the reaction usually uses basic solid powder as an acid binding agent to neutralize the HCl generated during the reaction.
  • the basic solid powder suitable for the present invention is not particularly limited, and may be, for example, one or more of sodium carbonate, magnesium carbonate, calcium carbonate, calcium oxide, magnesium oxide, magnesium hydroxide, and the like.
  • an excess of basic solid powder can be added in the first step of the reaction.
  • the excess value of the alkaline solid powder is not particularly limited, and for example, the excess may be 80% or less.
  • the reaction temperature in the first step is usually controlled at 0-35°C.
  • the first step reaction is usually carried out in a non-polar solvent, such as toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylbenzene, etc. Cyclohexane and other non-polar solvents.
  • the reaction time of the first step can be determined by monitoring the progress of the reaction.
  • the method for detecting the progress of the reaction may be known in the art, for example, gas chromatography (GC) or high performance liquid chromatography (HPLC) is used to detect whether the cyanuric chloride is completely reacted. After the reaction, the solid was filtered out to obtain a solution of Intermediate A.
  • GC gas chromatography
  • HPLC high performance liquid chromatography
  • an excess of NR 1 -p-phenylenediamine can be used. Compared with cyanuric chloride, NR 1 -p-phenylenediamine can generally exceed 20% or less. In certain embodiments, the excess of NR 1 -p-phenylenediamine is less than 10%.
  • the second step of the reaction usually uses lye as the acid binding agent.
  • an excess of lye is usually added.
  • the alkali in the lye can be excessively 20% or less or 10% or less relative to melamine.
  • the lye suitable for the present invention is not particularly limited, and may be, for example, sodium hydroxide solution, potassium hydroxide solution, triethylamine, triisopropylamine, N-isopropyldiethylamine, N,N-diisopropyl One or more of ethylamine, etc.
  • the lye is an aqueous solution of inorganic alkali (such as sodium hydroxide solution, potassium hydroxide solution)
  • its concentration is not particularly limited, and is usually 10% to 50% by weight, for example, 25% by weight.
  • the reaction temperature in the second step is usually controlled at 50-100°C.
  • the second step reaction is usually carried out in a non-polar solvent, such as toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylbenzene, etc. Cyclohexane and other non-polar solvents.
  • the reaction time of the second step can be determined by detecting the progress of the reaction, for example, using GC or HPLC to detect whether the content of NR 1 -p-phenylenediamine continues to decrease. After the reaction, after purification (for example, standing, separating the water phase, or washing with water), a solution of intermediate B is obtained.
  • an excess of NR 2 -p-phenylenediamine can be used. Compared with cyanuric chloride, NR 2 -p-phenylenediamine can generally exceed 20% or less. In certain embodiments, the excess of NR 2 -p-phenylenediamine is less than 10%.
  • the reaction temperature in the third step is usually controlled at 80-180°C.
  • the third step reaction is usually carried out in a non-polar solvent, such as toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylbenzene, etc. Cyclohexane and other non-polar solvents.
  • the reaction time of the third step can be determined by detecting the progress of the reaction, for example, using GC or HPLC to detect whether the content of NR 2 -p-phenylenediamine continues to decrease.
  • lye such as sodium hydroxide, potassium hydroxide solution, etc.
  • purification for example, separating the aqueous phase, washing the organic phase with water, distilling the organic solvent to obtain a crude product, recrystallization and purification of the crude product, and drying
  • the compound of formula (I) is obtained.
  • the combined reaction NR 1 - added in an amount of usually p-phenylenediamine NR 1 in the above-mentioned second step reaction - terephthalamide
  • the combined reaction is usually carried out in the form of stepwise temperature control, that is, first react at 50-100°C, and then react at 80-180°C.
  • the timing of switching the reaction temperature can be determined by detecting the progress of the reaction.
  • the temperature is switched from 50 to 100°C to 80 to 180 °C.
  • the combined reaction is usually carried out in a non-polar solvent, such as toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylcyclohexane, etc. It is carried out in non-polar solvents such as hexane.
  • the total time of the combined reaction can be determined by detecting the progress of the reaction, for example, using GC or HPLC to detect whether the content of NR 1 -p-phenylenediamine continues to decrease.
  • the combined reaction usually takes one of lye (such as sodium hydroxide solution, potassium hydroxide solution, triethylamine, triisopropylamine, N-isopropyldiethylamine, N,N-diisopropylethylamine, etc.) Or more) are acid binding agents.
  • lye can be added to neutralize and remove HCl, and after purification (for example, separating the water phase, washing the organic phase with water, distilling the organic solvent to obtain the crude product, recrystallization and purification of the crude product, and drying), the compound of formula (I) can be obtained.
  • the compound of the present invention can provide a rubber composition with better aging resistance and discoloration resistance. Therefore, the present invention also provides a rubber composition containing one or more of the compounds of formula I described herein. Generally, the rubber composition also contains a diene elastomer, a reinforcing filler, and a crosslinking agent.
  • Diene elastomer refers to an elastomer whose monomer contains a diene (such as butadiene, isoprene).
  • the diene elastomer suitable for the present invention can be various diene elastomers known in the art, including but not limited to natural rubber (NR), butadiene rubber (BR), isoprene rubber, styrene butadiene rubber (SBR) , Chloroprene rubber (CR), nitrile rubber (NBR), isoprene/butadiene copolymer, isoprene/styrene copolymer, isoprene/butadiene/styrene copolymer, etc. .
  • NR natural rubber
  • BR butadiene rubber
  • SBR styrene butadiene rubber
  • SBR styrene butadiene rubber
  • CR Chloroprene rubber
  • NBR nitrile
  • the diene elastomer is composed of natural rubber (such as SCR5) and butadiene rubber (such as BR9000); the mass ratio of natural rubber and butadiene rubber can be 1:9 to 9. :1, for example, 2:8 to 8:2, 3:7 to 7:3, 4:6 to 6:4, or 1:1.
  • the amount of the compound of formula I in the rubber composition is 0.1-5 parts by mass, for example, 1-5 parts by mass, 1.5-3.5 parts by mass, and 2-3 parts by weight.
  • the rubber composition may also contain other commonly used ingredients, including but not limited to reinforcing fillers, auxiliary agents, crosslinking agents and accelerators.
  • the dosages of reinforcing fillers, auxiliary agents, crosslinking agents and accelerators can be conventional dosages in this field.
  • the reinforcing filler may be carbon black, titanium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, clay, or talc. Generally, 40-60 parts by mass of reinforcing filler are used per 100 parts by mass of diene elastomer.
  • the auxiliary agent may be, for example, a softener used to improve processability.
  • the softener can be petroleum softeners such as aromatic oil, processing oil, lubricating oil, paraffin, liquid paraffin, petroleum pitch and petroleum jelly, etc., or fatty oil softeners 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.
  • the auxiliary agent can also be an active agent, such as zinc oxide, which can accelerate the vulcanization speed, improve the thermal conductivity of the rubber, wear resistance, and tear resistance.
  • additives are 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 stearic acid are used .
  • the crosslinking agent may be sulfur. Generally, 1 to 3 parts by mass of the crosslinking agent is used per 100 parts by mass of the diene elastomer.
  • the accelerator is usually a vulcanization accelerator, which can be sulfonamides, thiazoles, thiurams, thioureas, guanidines, dithiocarbamates, aldehyde amines, aldehyde ammonia, imidazolines and xanthogens At least one of acid vulcanization accelerators.
  • the accelerator may be the accelerator NS (N-tert-butyl-2-benzothiazole sulfenamide). Generally, 0.5-1.5 parts by mass of the accelerator is used per 100 parts by mass of the diene elastomer.
  • plasticizers can also be used in the rubber composition, such as DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate) , DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (o- Butyl benzyl phthalate), DWP (dilauryl phthalate) and DCHP (dicyclohexyl phthalate), etc.
  • the amount of plasticizer is a conventional amount in the field.
  • the rubber products of the present invention can be prepared by conventional methods. For example, it is prepared by two-stage mixing method, one-stage internal mixer mixing, mixing diene elastomers, reinforcing fillers, additives and antioxidants, debinding temperature above 110°C, two-stage open mixer mixing and mixing Glue with sulfur and accelerator.
  • the diene elastomer is first added to the thermomechanical mixer (such as internal mixer), after kneading for a certain period of time, adding reinforcing fillers, additives, antioxidants, and kneading until the mixing is uniform, reinforcing fillers, additives, antioxidants It can be added in batches, and 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, kneading again, and kneading During the period, the temperature is controlled below 110°C, such as 70°C; finally, vulcanization is performed to obtain vulcanized rubber.
  • the thermomechanical mixer such as internal mixer
  • the rubber composition obtained by kneading may be tableted before vulcanization.
  • the kneaded rubber composition can be vulcanized by conventional methods to obtain vulcanized rubber.
  • the vulcanization (curing) temperature is usually 130°C-200°C, such as 145°C.
  • the vulcanization time depends on the vulcanization temperature, vulcanization system and vulcanization kinetics. For 15-60 minutes, such as 30 minutes.
  • the compound of the present invention is used in rubber products, especially rubber tires, and can give rubber products or rubber tires more excellent anti-aging properties; in addition, compared with existing antioxidant products, rubber products or rubber tires containing the compound of the present invention It is not prone to surface pollution and discoloration, and has excellent discoloration resistance. Therefore, the present invention also provides a rubber product prepared by using the rubber composition described herein as a rubber component. Rubber products can be tires, rubber shoes, sealing strips, sound insulation boards, shock pads, etc.
  • the rubber article is a tire, such as the tread, belt, and sidewall of the tire. As the belt layer of the tire, in addition to the rubber composition described herein, the rubber product may also contain reinforcing materials conventionally used in the art.
  • the present invention also provides the application of the rubber composition described herein to improve the anti-aging performance and/or discoloration resistance of rubber or rubber products.
  • step (2) To the chlorobenzene solution of intermediate B22 obtained in step (2), 114g of N-isopropyl p-phenylenediamine (0.76 mol) was added, and the temperature was raised to 80°C for the reaction. GC was used to detect when the N-isopropyl p-phenylene When the diamine content no longer decreases, the temperature is lowered, the reaction is stopped, 112.6 g of sodium hydroxide solution (25 wt%) is added for neutralization, the organic phase is washed with water, and chlorobenzene is distilled to obtain a crude product.
  • Test Examples 1-6 were prepared according to the formula shown in Table 1, specifically including the following steps:
  • the obtained rubber composition is calendered into a sheet (with a thickness of 2-3mm) and vulcanized at a vulcanization temperature of 145°C and a time of 30 minutes.
  • N550 Cabot Corporation carbon black N550
  • Aromatic oil Shanghai Titan Technology Co., Ltd. general reagent
  • Zinc oxide Shanghai Titan Technology Co., Ltd. general reagent zinc oxide (AR);
  • NS Vulcanization accelerator NS of Shengao Chemical Technology Co., Ltd.;
  • Compound I-12 The compound synthesized in Example 12.
  • Test case 1 Test case 2
  • Test case 3 Test case 4
  • Test case 5 Test case 6
  • test pieces of various rubber compositions were subjected to an ozone deterioration test. After 39 hours, the deterioration state of the test piece was checked.
  • the anti-ozone performance level is based on the density of cracks formed, and its evaluation criteria are:

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Abstract

提供一种具有抗老化和耐变色功效的化合物及其制备方法。所述化合物具有如下式(I)结构，式中，R、R 1和R 2如文中所定义。所述化合物相比现有防老剂产品具有更加长效的抗老化性能，且具有耐变色性能，可作为防老剂用于橡胶制品、尤其橡胶轮胎中，可以防止橡胶制品或橡胶轮胎在使用过程中由于光、热、氧、疲劳等引起的老化劣化。

Description

具有抗老化和耐变色功效的化合物及其制备方法 技术领域
本发明属于橡胶助剂领域，具体涉及具有抗老化和耐变色功效的化合物及其制备方法。
背景技术
目前，橡胶制品尤其是轮胎制品，通常使用对苯二胺类化合物作为抗老化剂。其中，二烷基对苯二胺、烷基芳基对苯二胺和二芳基对苯二胺等衍生物使用较为广泛，包括N-(1,3-二甲基丁基)-N’-苯基对苯二胺(简称6PPD或4020)、N-异丙基-N’-苯基对苯二胺(简称IPPD)、N,N’-双(1,4-二甲基戊基)对苯二胺(简称77PD)、二苯基对苯二胺类混合物(简称防老剂3100或DTPD)等。
现有防老剂产品虽在轮胎等领域的抗老化方面具有比较显著的效果，但橡胶制品或轮胎中的防老剂会因其自身在使用过程中变色而很快迁移至橡胶制品或轮胎表面，进而导致橡胶制品或轮胎表面污染变色、受损等；同时，由于防老剂迁移至轮胎等橡胶制品的表面速度过快，进而导致制品中的防老剂含量迅速减少，故其持久防护性能就会相对比较差。
近年来，随着绿色可持续经济发展要求的提升，用户对轮胎的抗老化持久性和表面变色等问题的关注度也越来越高。因此，开发出比现有防老剂产品具有更加长效的抗老化性能且耐变色的防老剂，具有更加迫切的需要。
发明内容
基于现有技术存在的上述问题，本发明提供一系列具有抗老化和耐变色功效的化合物及其制备方法。本发明的化合物具有更加长效的抗老化性能，且具有耐变色性能，可作为防老剂用于橡胶制品、尤其橡胶轮胎中，可以防止橡胶制品或橡胶轮胎在使用过程中由于光、热、氧、疲劳等引起的老化劣化。
具体而言，本发明提供下式(I)所示的化合物：
Figure PCTCN2020125100-appb-000001
其中，
R为C3～C16烷基、C3～C10环烷基取代的C3～C16烷基、C3～C10环烷基、或C3～C16烷基取代的C3～C10环烷基；
R 1和R 2相同或不同，各自独立选自C3～C10烷基、C3～C10环烷基或C6～C14芳基取代的C3～C10烷基、C3～C10环烷基、C3～C10烷基取代的C3～C10环烷基、C6～C14芳基、和C3～C10烷基取代的C6～C14芳基。
在一个或多个实施方案中，R为C3～C10烷基或C3～C10环烷基，优选为C3～C10支链烷基或C3～C10环烷基，更优选为异丙基、叔丁基、叔辛基或环己基。
在一个或多个实施方案中，R 1和R 2相同或不同，各自独立为C3～C10烷基或苯基，优选各自独立为C3～C10支链烷基或苯基，更优选各自独立为异丙基、1,4-二甲基戊基或苯基。
在一个或多个实施方案中，所述化合物选自：
Figure PCTCN2020125100-appb-000002
Figure PCTCN2020125100-appb-000003
Figure PCTCN2020125100-appb-000004
Figure PCTCN2020125100-appb-000005
本发明还提供一种制备本发明任一实施方案所述的化合物的方法，包括：
(1)使三聚氯氰与NH 2R反应，制备得到下式所示的中间体A：
Figure PCTCN2020125100-appb-000006
(2)使中间体A与N-R 1-对苯二胺反应，制备得到下式所示的中间体B：
Figure PCTCN2020125100-appb-000007
(3)使中间体B与N-R 2-对苯二胺反应，制备得到式(I)化合物：
Figure PCTCN2020125100-appb-000008
其中，式A、式B和式(I)化合物中的R、R 1和R 2如本发明任一实施方案所定义。
在一个或多个实施方案中，步骤(1)的反应中添加碱性固体粉末，反应温度为0～35℃。
在一个或多个实施方案中，步骤(2)的反应中添加碱液，反应温度为50～100℃。
在一个或多个实施方案中，步骤(3)的反应温度为80～180℃。
在一个或多个实施方案中，R 1和R 2相同，所述步骤(2)和步骤(3)合并为步骤(2’)：使中间体A和N-R 1-对苯二胺反应，制备得到式(I)化合物。
在一个或多个实施方案中，步骤(2’)的反应中添加碱液，反应先在50～100℃下进行，然后在80～180℃下进行。
本发明还提供一种橡胶组合物，所述橡胶组合物含有本发明任一实施方案所述的化合物。
本发明还提供一种橡胶制品，所述橡胶制品采用本发明任一实施方案所述的橡胶组合物作为橡胶组分制备得到；优选地，所述橡胶制品为轮胎。
本发明还提供本发明任一实施方案所述的化合物在提高橡胶或橡胶制品的抗老化性能和/或耐变色性能中的用途；优选地，所述橡胶制品为轮胎。
具体实施方式
为使本领域技术人员可了解本发明的特点及效果，以下仅就说明书及权利要求书中提及的术语及用语进行一般性的说明及定义。除非另有指明，否则文中使用的所有技术及科学上的字词，均为本领域技术人员对于本发明所了解的通常意义，当有冲突情形时，应以本说明书的定义为准。
本文描述和公开的理论或机制，无论是对或错，均不应以任何方式限制本发明的范围，即本发明内容可以在不为任何特定的理论或机制所限制的情况下实施。
在本文中，所有以数值范围或百分比范围形式界定的特征如数值、数量、含量与浓度仅是为了简洁及方便。据此，数值范围或百分比范围的描述应视为已涵盖且具体公开所有可能的次级范围及范围内的个别数值(包括整数与分数)。
本文中，为使描述简洁，未对各个实施方案或实施例中的各个技术特征的所有可能的组合都进行描述。因此，只要这些技术特征的组合不存在矛盾，各个实施方案或实施例中的各个技术特征可以进行任意的组合，所有可能的组合都应当认为是本说明书记载的范围。
本文中，烷基是指直链或支链单价饱和烃基，通常含有1～16个碳原子(C1～C16烷基)，优选含有3～16个碳原子(C3～C16烷基)。烷基的例子包括但不限于甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、1,4-二甲基戊基和叔辛基。本文中，烷基可任选地被芳基或环烷基取代，通常取代基的数量为1个。取代的烷基的例子包括但不限于环己基甲基、苯甲基和苯乙基。
本文中，亚烷基是指直链或支链二价饱和烃基，通常含有1～16个碳原子(C1～C16亚烷基)，优选含有3～16个碳原子(C3～C16亚烷基)。亚烷基的例子包括但不限于亚甲基、亚乙基和1,3-亚丙基。
本文中，环烷基是指含有3～10个碳原子，优选含有3～8个碳原子的单价饱和烃环。环烷基的例子包括但不限于环丙基、环丁基、环戊基、环己基、环 庚基、环辛基和金刚烷基。本文中，环烷基可任选地被烷基取代。取代基的数量可以是1或2个。取代的环烷基的例子包括但不限于甲基环己基。
本文中，亚环烷基是指含有3～10个碳原子，优选含有3～8个碳原子的二价饱和烃环。亚环烷基的例子包括但不限于1,2-环戊二基和1,2-环己二基。
本文中，芳基指芳烃分子的芳核碳上去掉一个氢原子后剩下的一价基团。芳基的环碳原子数通常为6～14个。示例性的芳基包括苯基和萘基。芳基可任选地被烷基、环烷基和/或芳基取代。取代基的数量通常为1或2个。示例性的取代的芳基的例子包括但不限于2-甲基苯基、4-环己基苯基、4-(2-甲基环己基)苯基和4-联苯基。
本发明发现具有如式(I)所示结构的化合物可以提供比常规防老剂更好的耐候性、持久性以及耐变色性等性能，其具体结构如下：
Figure PCTCN2020125100-appb-000009
其中，R为C3～C16烷基、C3～C10环烷基取代的C3～C16烷基、C3～C10环烷基、或C3～C16烷基取代的C3～C10环烷基；
R 1和R 2相同或不同，各自独立选自C3～C10烷基、C3～C10环烷基或C6～C14芳基取代的C3～C10烷基、C3～C10环烷基、C3～C10烷基取代的C3～C10环烷基、C6～C14芳基、和C3～C10烷基取代的C6～C14芳基。
优选的R为C3～C10烷基或C3～C10环烷基。在某些实施方案中，R为C3～C10烷基，优选为C3～C10支链烷基或C3～C10环烷基，例如异丙基、叔丁基、叔辛基或环己基。
优选的R 1和R 2各自独立为C3～C10烷基或苯基。在优选的实施方案中，R 1和R 2各自独立为C3～C10支链烷基或苯基。在某些实施方案中，R 1和R 2各自独立为异丙基、1,4-二甲基戊基或苯基。
在某些实施方案中，R为叔丁基或叔辛基，R 1和R 2各自独立为1,4-二甲基戊基或苯基。
本发明的式(I)所示结构的化合物可分三步来制备：
第一步，以三聚氯氰(TCT)和NH 2R为反应原料来制备中间体A，其中，R为C3～C16烷基、C3～C10环烷基取代的C3～C16烷基、C3～C10环烷基或C3～C16烷基取代的C3～C10环烷基；
Figure PCTCN2020125100-appb-000010
第二步，中间体A再和N-R 1-对苯二胺反应，制备中间体B，其中，R 1为C3～C10烷基、C3～C10环烷基或C6～C14芳基取代的C3～C10烷基、C3～C10环烷基、C3～C10烷基取代的C3～C10环烷基、C6～C14芳基或C3～C10烷基取代的C6～C14芳基；
Figure PCTCN2020125100-appb-000011
第三步，中间体B再和N-R 2-对苯二胺反应，制备目标产物式(I)化合物，其中，R 2为C3～C10烷基、C3～C10环烷基或C6～C14芳基取代的C3～C10烷基、C3～C10环烷基、C3～C10烷基取代的C3～C10环烷基、C6～C14芳基或C3～C10烷基取代的C6～C14芳基；
Figure PCTCN2020125100-appb-000012
其中，中间体A、中间体B和式(I)化合物中优选的R、R 1和R 2可以如本文任一实施方案所述。
第一步中，为了提高三聚氯氰的转化率，可使用过量的NH 2R。相对于三聚氯氰来说，NH 2R一般可过量10％以下。在某些实施方案中，NH 2R过量8％以下或5％以下。本文中，如无特别说明，某一物质过量是指该物质的添加量大于三聚氯氰的添加量。本文以物质的量计过量的百分比值，例如当使用1mol三聚氰氯时，NH 2R过量10％以下是指可使用1mol～1.1mol的NH 2R。
第一步反应通常以碱性固体粉末为缚酸剂，用来中和反应过程中产生的HCl。适用于本发明的碱性固体粉末不受特别限制，例如可以是碳酸钠、碳酸镁、碳酸钙、氧化钙、氧化镁、氢氧化镁等中的一种或多种。通常，为了更好地中和HCl，第一步反应中可添加过量的碱性固体粉末。相对于三聚氯氰而言，碱性固体粉末的过量值不受特别限制，例如可过量80％以下。
第一步反应温度通常控制在0～35℃。第一步反应通常在非极性溶剂中进行，例如可以在甲苯、二甲苯、三甲苯、氯苯、甲基环己烷、二氯苯、三氯苯、二甲基环己烷、三甲基环己烷等非极性溶剂中进行。第一步反应的时间可通过检测反应进程来确定。本文中，检测反应进程的方法可以是本领域已知的，例如利用气相色谱(GC)或高效液相色谱(HPLC)检测三聚氯氰是否完全反应掉。反应后过滤出固体，得到中间体A的溶液。
第二步中，为了提高中间体A的转化率，可使用过量的N-R 1-对苯二胺。相对于三聚氯氰而言，N-R 1-对苯二胺一般可过量20％以下。在某些实施方案中，N-R 1-对苯二胺过量10％以下。
第二步反应通常以碱液为缚酸剂。第二步中通常添加过量的碱液，例如碱液中的碱相对于三聚氰胺而言可过量20％以下或10％以下。适用于本发明的碱液不受特别限制，例如可以是氢氧化钠溶液、氢氧化钾溶液、三乙胺、三异丙胺、N-异丙基二乙胺、N,N-二异丙基乙胺等中的一种或多种。本发明中，碱液为无机碱的水溶液(如氢氧化钠溶液、氢氧化钾溶液)时，其浓度不受特别限制，通常为10wt％～50wt％，例如可以是25wt％。
第二步反应温度通常控制在50～100℃。第二步反应通常在非极性溶剂中进行，例如可以在甲苯、二甲苯、三甲苯、氯苯、甲基环己烷、二氯苯、三氯苯、二甲基环己烷、三甲基环己烷等非极性溶剂中进行。第二步反应的时间可通过检测反应进程来确定，例如利用GC或HPLC检测N-R 1-对苯二胺的含量是否继续降低。反应后，经过纯化(例如静置、分去水相，或水洗)，得到中间体B的溶液。
第三步中，为了提高中间体B的转化率，可使用过量的N-R 2-对苯二胺。相对于三聚氯氰而言，N-R 2-对苯二胺一般可过量20％以下。在某些实施方案中，N-R 2-对苯二胺过量10％以下。
第三步反应温度通常控制在80～180℃。第三步反应通常在非极性溶剂中进行，例如可以在甲苯、二甲苯、三甲苯、氯苯、甲基环己烷、二氯苯、三氯苯、二甲基环己烷、三甲基环己烷等非极性溶剂中进行。第三步反应的时间可通过检测反应进程来确定，例如利用GC或HPLC检测N-R 2-对苯二胺的含量是否继续降低。反应结束后加入碱液(如氢氧化钠、氢氧化钾溶液等)进行中和除去HCl。中和后，经过纯化(例如分去水相，有机相水洗，有机物蒸馏溶剂得到粗品，粗品重结晶提纯，干燥)，得到式(I)化合物。
当式(I)所示结构的化合物的R 1和R 2相同时，上述制备方法中的第二步和第三步可合并为一步进行，即，使中间体A和N-R 1-对苯二胺反应，制备得到式(I)化合物。
在第二步和第三步合并为一步进行(下称合并反应)的实施方案中，合并反应中N-R 1-对苯二胺的添加量通常为上述第二步反应中N-R 1-对苯二胺的添加量和第三步反应中N-R 2-对苯二胺的添加量之和。合并反应通常采用分段控 温的形式进行，即先在50～100℃下反应，后在80～180℃下反应。可通过检测反应进程来确定切换反应温度的时机，例如当利用GC或HPLC检测到N-R 1-对苯二胺的含量降低到添加量的一半时，将温度由50～100℃切换到80～180℃。合并反应通常在非极性溶剂中进行，例如可以在甲苯、二甲苯、三甲苯、氯苯、甲基环己烷、二氯苯、三氯苯、二甲基环己烷、三甲基环己烷等非极性溶剂中进行。合并反应的总时间可通过检测反应进程来确定，例如利用GC或HPLC检测N-R 1-对苯二胺的含量是否继续降低。合并反应通常以碱液(如氢氧化钠溶液、氢氧化钾溶液、三乙胺、三异丙胺、N-异丙基二乙胺、N,N-二异丙基乙胺等中的一种或多种)为缚酸剂。反应结束后，可加入碱液进行中和除去HCl，经过纯化(例如分去水相，有机相水洗，有机物蒸馏溶剂得到粗品，粗品重结晶提纯，干燥)，得到式(I)化合物。
本发明的化合物可为橡胶组合物提供更好的耐老化性能和耐变色性能。因此，本发明也提供一种橡胶组合物，该橡胶组合物含有本文所述式I化合物中的一种或多种。通常，橡胶组合物还含有二烯弹性体、增强填料和交联剂。
二烯弹性体是指单体包含二烯烃(如丁二烯、异戊二烯)的弹性体。适用于本发明的二烯弹性体可以是本领域已知的各种二烯弹性体，包括但不限于天然橡胶(NR)、顺丁橡胶(BR)、异戊橡胶、丁苯橡胶(SBR)、氯丁橡胶(CR)、丁腈橡胶(NBR)、异戊二烯/丁二烯共聚物、异戊二烯/苯乙烯共聚物、异戊二烯/丁二烯/苯乙烯共聚物等。在某些实施方案中，本发明的橡胶组合物中，二烯弹性体由天然橡胶(如SCR5)和顺丁橡胶(如BR9000)组成；天然橡胶和顺丁橡胶的质量比可以为1：9到9：1，例如为2：8到8：2、3：7到7：3、4：6到6：4、或1：1。
通常，以100质量份二烯弹性体为基准，橡胶组合物中式I化合物的用量为0.1-5质量份，例如1～5质量份、1.5～3.5质量份、2～3重量份。
橡胶组合物中还可含有其它常用的成分，包括但不限于增强填料、助剂、交联剂和促进剂等。本发明中，增强填料、助剂、交联剂和促进剂的用量可以是本领域的常规用量。
增强填料可以是炭黑、氧化钛、氧化镁、碳酸钙、碳酸镁、氢氧化铝、氢氧化镁、粘土或滑石等。通常，每100质量份的二烯弹性体使用40-60质量份的增强填料。
助剂可以是，例如为了改善加工性而使用的软化剂。软化剂可以为石油类软化剂如芳烃油、加工油、润滑油、石蜡、液体石蜡、石油沥青和凡士林等，也可以为脂肪油类软化剂如蓖麻油、亚麻籽油、菜籽油、椰子油、蜡(如蜂蜡、巴西棕榈蜡和羊毛脂)、妥尔油、亚油酸、棕榈酸、硬脂酸和月桂酸等。助剂还可以是活性剂，例如氧化锌，可以起到加快硫化速度、提高橡胶导热性、耐磨性、耐撕裂性等作用。通常，每100质量份的二烯弹性体使用5-20质量份的助剂，例如使用2-8质量份的芳烃油、2-8质量份的氧化锌和1-4质量份的硬脂酸。
交联剂可以是硫磺。通常，每100质量份的二烯弹性体使用1-3质量份的交联剂。
促进剂通常为硫化促进剂，可以为磺胺类、噻唑类、秋兰姆类、硫脲类、胍类、二硫代氨基甲酸盐类、醛胺类、醛氨类、咪唑啉类和黄原酸类硫化促进剂的至少一种。例如，促进剂可以是促进剂NS(N-叔丁基-2-苯并噻唑次磺酰胺)。通常，每100质量份的二烯弹性体使用0.5-1.5质量份的促进剂。
另外，在需要时，橡胶组合物中还可使用增塑剂，例如DMP(邻苯二甲酸二甲酯)、DEP(邻苯二甲酸二乙酯)、DBP(邻苯二甲酸二丁酯)、DHP(邻苯二甲酸二庚酯)、DOP(邻苯二甲酸二辛酯)、DINP(邻苯二甲酸二异壬酯)、DIDP(邻苯二甲酸二异癸酯)、BBP(邻苯二甲酸丁基苄基酯)、DWP(邻苯二甲酸二月桂酯)和DCHP(邻苯二甲酸二环己酯)等。增塑剂的用量为本领域的常规用量。
可采用常规的方法制备本发明的橡胶制品。例如，采用两段混炼方式进行制备，一段密炼机混炼，混合二烯弹性体、增强填料、助剂和防老剂，排胶温度110℃以上，二段开炼机混炼，混炼胶与硫磺和促进剂。
通常，先向热机械混合器(如密炼机)中加入二烯弹性体，捏合一定时间后，加入增强填料、助剂、防老剂，继续捏合直至混合均匀，增强填料、助剂、 防老剂可以分批加入，捏合期间温度控制在110℃至190℃之间，优选在150℃至160℃之间；然后，将混合物冷却至100℃以下，加入交联剂和促进剂，再次捏合，捏合期间温度控制在110℃以下，如70℃；最后进行硫化，即可制得硫化橡胶。可选地，在硫化前可对捏合得到的橡胶组合物进行压片。可采用常规的方法对捏合好的橡胶组合物进行硫化，得到硫化橡胶，硫化(固化)温度通常为130℃-200℃，如145℃，硫化时间取决于硫化温度、硫化体系和硫化动力学，通常为15-60分钟，如30分钟。
本发明的化合物用于橡胶制品，尤其橡胶轮胎中，可赋予橡胶制品或橡胶轮胎更加优异的抗老化性能；此外，相比现有的防老剂产品，含有本发明的化合物的橡胶制品或橡胶轮胎不易发生表面污染变色，具有优异的耐变色性能。因此，本发明还提供一种橡胶制品，所述橡胶制品采用本文所述的橡胶组合物作为橡胶组分制备得到。橡胶制品可以是轮胎、胶鞋、密封条、隔音板、止震垫等。在某些实施方案中，橡胶制品为轮胎，例如轮胎的胎面、带束层和胎侧。作为轮胎的带束层，除本文所述的橡胶组合物外，所述橡胶制品还可含有本领域常规使用的增强材料。本发明还提供本文所述的橡胶组合物在提高橡胶或橡胶制品的抗老化性能和/或耐变色性能中的应用。
下文将以具体实施例的方式阐述本发明。应理解，这些实施例仅仅是阐述性的，并非意图限制本发明的范围。实施例中所用到的方法、试剂和材料，除非另有说明，否则为本领域常规的方法、试剂和材料。制备例中的原料化合物均可通过市售途径购得。
制备例1：2-异丙胺-4,6-二(4-苯胺基苯胺)-1,3,5-三嗪(化合物I-1)的制备
(1)中间体A1的合成
称取118.1g三聚氯氰(0.64mol)溶于360g甲苯中，加入74.2g碳酸钠固体粉末，在10℃剧烈搅拌条件下滴加39.6g异丙胺的甲苯溶液(0.67mol异丙胺+80g甲苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A1的无色透明溶液。
(2)中间体B11的合成
称取142.6g N-苯基对苯二胺(0.77mol)溶于180g甲苯中，升温至65℃，剧烈搅拌下滴加步骤(1)中得到的中间体A1的甲苯溶液，同时滴加112.6g氢氧化钠溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当N-苯基对苯二胺含量不再降低时，停止反应，静置，分去水相，得到含中间体B11的甲苯溶液。
(3)化合物I-1的合成
向步骤(2)中得到的中间体B11的甲苯溶液中加入132.5g N-苯基对苯二胺(0.72mol)，升温至80℃反应，用GC检测，当N-苯基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，分去水相，有机相水洗后蒸馏甲苯，得到粗品。然后用石油醚重结晶，干燥后得到289.2g(收率90％)2-异丙胺-4,6-二(4-苯胺基苯胺)-1,3,5-三嗪(化合物I-1)。
Figure PCTCN2020125100-appb-000013
化合物I-1的性状：蓝色固体。
1H-HMR(400MHz,DMSO-D 6,δppm)：8.71(s,2H),7.93(s,2H),7.64(br,4H),7.17(t,4H),6.99(q,8H),6.73(t,2H),6.31(s,1H),3.4(s,1H),1.41(s,6H)。
制备例2：2-异丙胺-4,6-二(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-2)的制备
(1)中间体A1的合成
称取118.1g三聚氯氰(0.64mol)溶于360g二甲苯中，加入71.2g超细碳酸钙固体粉末，在10℃剧烈搅拌条件下滴加38.4g异丙胺的二甲苯溶液(0.65mol异丙胺+80g二甲苯)，滴加1.5h，滴完后继续反应1.5h，取样进行 GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A1的无色透明溶液。
(2)中间体B12的合成
称取152.4g N-1,4-二甲基戊基对苯二胺(0.74mol)溶于180g二甲苯中，升温至70℃，剧烈搅拌下滴加步骤(1)中得到的中间体A1的二甲苯溶液，同时滴加157.6g氢氧化钾溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当N-1,4-二甲基戊基对苯二胺含量不再降低时，停止反应，静置，分去水相，得到含中间体B12的二甲苯溶液。
(3)化合物I-2的合成
向步骤(2)中得到的中间体B12的二甲苯溶液中加入152.5g N-1,4-二甲基戊基对苯二胺(0.74mol)，升温至110℃反应，用GC检测，当N-1,4-二甲基戊基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，有机相水洗后蒸馏二甲苯，得到粗品。然后用石油醚重结晶，干燥后得到283g(收率81％)2-异丙胺-4,6-二(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-2)。
Figure PCTCN2020125100-appb-000014
化合物I-2的性状：紫褐色固体。
1H-HMR(400MHz,DMSO-D6,δppm)：8.39(s,2H),7.32(d,4H),6.48(d,4H),6.09(S,1H),4.92(t,3H),3.31-3.21(m,2H),1.56-1.43(m,4H),1.42-1.13(m,12H),1.06(d,6H),0.85(q,12H)。
制备例3：2-叔丁胺-4,6-二(4-苯胺基苯胺)-1,3,5-三嗪(化合物I-3)的制备
(1)中间体A2的合成
称取118.1g三聚氯氰(0.64mol)溶于360g三甲苯中，加入71.2g超细碳酸镁固体粉末，在15℃剧烈搅拌条件下滴加49.1g叔丁胺的三甲苯溶液(0.67mol叔丁胺+80g甲苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A2的无色透明溶液。
(2)中间体B21的合成
称取131.5g N-苯基对苯二胺(0.71mol)溶于180g三甲苯中，升温至65℃，剧烈搅拌下滴加步骤(1)中得到的中间体A2的三甲苯溶液，同时滴加71.1g三乙胺，滴加1～2h，保温1h，取样GC检测，当N-苯基对苯二胺含量不再降低时，停止反应，水洗，得到含中间体B21的三甲苯溶液。
(3)化合物I-3的合成
向步骤(2)中得到的中间体B21的三甲苯溶液中加入123.3g N-苯基对苯二胺(0.67mol)，升温至105℃反应，用GC检测，当N-苯基对苯二胺含量不再降低时，降温，停止反应，加入71.1g三乙胺中和，水洗后蒸馏三甲苯，得到粗品。然后用石油醚重结晶，干燥后得到280g(收率85％)2-叔丁胺-4,6-二(4-苯胺基苯胺)-1,3,5-三嗪(化合物I-3)。
Figure PCTCN2020125100-appb-000015
化合物I-3的性状：深蓝色固体。
1H-NMR(400MHz,DMSO-D6,δPPm)：8.71(s,2H),7.93(s,2H),7.64(br,4H),7.17(t,4H),6.99(q,8H),6.73(t,2H),6.31(s,1H),1.41(s,9H)。
制备例4：2-叔丁胺-4,6-二(4-异丙胺基苯胺)-1,3,5-三嗪(化合物I-4)的制备
(1)中间体A2的合成
称取118.1g三聚氯氰(0.64mol)溶于360g氯苯中，加入64g氧化钙固体粉末，在15℃剧烈搅拌条件下滴加49.1g叔丁胺的甲苯溶液(0.67mol叔丁胺+80g氯苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A2的无色透明溶液。
(2)中间体B22的合成
称取105g N-异丙基对苯二胺(0.7mol)溶于180g氯苯中，升温至60℃，剧烈搅拌下滴加步骤(1)中得到的中间体A2的氯苯溶液，同时滴加100.5g三异丙胺，滴加1～2h，保温1h，取样GC检测，当N-异丙基对苯二胺含量不再降低时，停止反应，静置，分去水相，得到含中间体B22的氯苯溶液。
(3)化合物I-4的合成
向步骤(2)中得到的中间体B22的氯苯溶液中加入114g N-异丙基对苯二胺(0.76mol)，升温至80℃反应，用GC检测，当N-异丙基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，有机相水洗后蒸馏氯苯，得到粗品。然后用石油醚重结晶，干燥后得到258g(收率90％)2-叔丁胺-4,6-二(4-异丙胺基苯胺)-1,3,5-三嗪(化合物I-4)。
Figure PCTCN2020125100-appb-000016
化合物I-4的性状：紫褐色固体。
1H-HMR(400MHz,DMSO-D6,δppm)：8.29(s,2H),7.33(d,4H),6.44(d,4H),6.02(S,1H),4.92(d,2H),3.4(d,2H),1.42-1.13(m,9H),0.85(q,12H)。
实施例5：2-叔丁胺-4,6-二(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-5)
(1)中间体A2合成
称取118.1g三聚氯氰(0.64mol)溶于360g二氯苯中，加入38.4g超细氧化镁固体粉末，在20℃剧烈搅拌条件下滴加51.3g叔丁胺的二氯苯溶液(0.7mol叔丁胺+80g二氯苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A2为无色透明溶液。
(2)中间体B23合成
称取144.2g N-1,4-二甲戊基对苯二胺(0.7mol)溶于180g二氯苯中，升温至70℃，剧烈搅拌下滴加步骤(1)中得到的中间体A2的二氯苯溶液，同时滴加157.6g氢氧化钾溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当N-1,4-二甲戊基对苯二胺含量不再降低时停止反应，静置，分去水相，得到含中间体B23二氯苯溶液。
(3)化合物I-5的合成
向步骤(2)中得到的中间体B23二氯苯溶液中加入148.4g N-1,4-二甲戊基对苯二胺(0.72mol)，升温至150℃反应，用GC检测，当N-1,4-二甲戊基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，得到粗品。然后用石油醚重结晶，干燥后得到286.7g(收率80％)2-叔丁胺-4,6-二(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-5)。
Figure PCTCN2020125100-appb-000017
化合物I-5的性状：深紫色固体。
1H-NMR(400MHz,DMSO-D6,δppm)：8.29(s,2H),7.33(d,4H),6.44(d,4H),6.02(S,1H),4.92(d,2H),3.31-3.21(m,2H),1.56-1.43(m,4H),1.42-1.13(m,15H),1.06(d,6H),0.85(q,12H)。
制备例6：2-叔丁胺-4-(4-苯胺基苯胺)-6-(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-6)
(1)中间体A2的合成
称取118.1g三聚氯氰(0.64mol)溶于360g甲基环己烷中，加入71.2g超细氢氧化镁固体粉末，在20℃剧烈搅拌条件下滴加49.1g叔丁胺的甲基环己烷溶液(0.67mol叔丁胺+80g甲基环己烷)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A2的无色透明溶液。
(2)中间体B21的合成
称取124.0g N-苯基对苯二胺(0.67mol)溶于180g甲基环己烷中，升温至50℃，剧烈搅拌下滴加步骤(1)中得到的中间体A2的甲基环己烷溶液，同时滴加157.6g氢氧化钾溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当N-苯基对苯二胺含量不变时，停止反应，水洗，得到含中间体B21的甲基环己烷溶液。
(3)化合物I-6的合成
向步骤(2)中得到的中间体B21的甲基环己烷溶液中加入131.9g N-1,4-二甲戊基对苯二胺(0.64mol)，升温至160℃反应，用GC检测，当N-1,4-二甲戊基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠(25wt％)中和，水洗后蒸馏甲基环己烷，得到粗品。然后用石油醚重结晶，干燥后得到261.7g(收率76％)2-叔丁胺-4-(4-苯胺基苯胺)-6-(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-6)。
Figure PCTCN2020125100-appb-000018
化合物I-6性状：深紫色固体。
1H-NMR(400MHz,DMSO-D6,δPPm)：8.56(d,2H),7.90(s,1H),7.68(d,2H),7.39(d,2H),7.21(t,2H),7.02(t,4H),6.79(t,1H),6.52(d,2H),6.22(s,1H),5.0(d, 1H),3.37(m,1H),1.6-1.45(m,2H),1.43(s,9H),1.31-1.18(m,3H),1.11(d,3H),0.89(q,6H)。
实施例7：2-叔辛胺-4,6-二(4-苯胺基苯胺)-1,3,5-三嗪(化合物I-7)
(1)中间体A3的合成
称取118.1g三聚氯氰(0.64mol)溶于360g三氯苯中，加入71.2g碳酸钠固体粉末，在30℃剧烈搅拌条件下滴加86.5g叔辛胺的三氯苯溶液(0.67mol叔辛胺+80g三氯苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A3的无色透明溶液。
(2)中间体B31的合成
称取129.6g N-苯基对苯二胺(0.7mol)溶于180g三氯苯中，升温至70℃，剧烈搅拌下滴加步骤(1)中得到的中间体A3的三氯苯溶液，同时滴加157.6g氢氧化钾(25wt％)，滴加1～2h，保温1h，取样GC检测，当N-苯基对苯二胺含量不再降低时，停止反应，静置，分去水相，得到含中间体B31的三氯苯溶液。
(3)化合物I-7的合成
向步骤(2)中得到的中间体B31的三氯苯溶液中加入136.2g N-苯基对苯二胺(0.74mol)，升温至105℃反应，用GC检测，当N-苯基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，分去水相，有机相蒸馏三氯苯，得到粗品。然后用石油醚重结晶，干燥后得到322.1g(收率88％)2-叔辛胺-4,6-二(4-苯胺基苯胺)-1,3,5-三嗪(化合物I-7)。
Figure PCTCN2020125100-appb-000019
化合物I-7的性状：蓝褐色固体。
1H-NMR(400MHz,DMSO-D6,δppm)：8.6(d,2H),7.95(s,2H),7.63(s,4H),7.16(t,4H),6.99(q,8H),6.72(t,2H),6.17(br,1H),1.9(s,2H),1.42(s,6H),0.96(s,9H)。
实施例8：2-叔辛胺-4,6-二(4-异丙胺基苯胺)-1,3,5-三嗪(化合物I-8)
(1)中间体A3的合成
称取118.1g三聚氯氰(0.64mol)溶于360g二甲基环己烷中，加入71.2g超细碳酸钠固体粉末，在30℃剧烈搅拌条件下滴加86.5g叔辛胺的二甲基环己烷溶液(0.67mol叔辛胺+80g二甲基环己烷)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A3的无色透明溶液。
(2)中间体B32的合成
称取105g N-异丙基对苯二胺(0.7mol)溶于180g二甲基环己烷中，升温至65℃，剧烈搅拌下滴加步骤(1)中得到的中间体A3的二甲基环己烷溶液，同时滴加112.6g氢氧化钠溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当N-异丙基对苯二胺含量不再降低时，停止反应，静置，分去水相，得到含中间体B32的二甲基环己烷溶液。
(3)化合物I-8的合成
向步骤(2)中得到的中间体B32的二甲基环己烷溶液中加入108g N-异丙基对苯二胺(0.72mol)，升温至90℃反应，用GC检测，当N-异丙基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，有机相水洗后蒸馏二甲基环己烷，得到粗品。然后用石油醚重结晶，干燥后得到293.5g(收率91％)2-叔辛胺-4,6-二(4-异丙胺基苯胺)-1,3,5-三嗪(化合物I-8)。
Figure PCTCN2020125100-appb-000020
化合物I-8的性状：紫褐色固体。
1H-HMR(400MHz,DMSO-D6,δppm)：8.29(s,2H),7.33(d,4H),6.44(d,4H),6.02(S,1H),4.92(d,2H),3.4(d,2H),1.9(s,2H),1.42-1.13(m,18H),0.96(s,9H)。
实施例9：2-叔辛胺-4-(4-苯胺基苯胺)-6-(4-异丙胺基苯胺)-1,3,5-三嗪(化合物I-9)
(1)中间体A3的合成
称取118.1g三聚氯氰(0.64mol)溶于360g三甲基环己烷中，加入71.2g碳酸钠固体粉末，在35℃剧烈搅拌条件下滴加86.5g叔辛胺的三甲基环己烷溶液(0.67mol叔辛胺+80g三甲基环己烷)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A3的无色透明溶液。
(2)中间体B31的合成
称取129.6g N-苯基对苯二胺(0.7mol)溶于180g三甲基环己烷中，升温至70℃，剧烈搅拌下滴加步骤(1)中得到的中间体A3的三甲基环己烷溶液，同时滴加157.6g氢氧化钾(25wt％)，滴加1～2h，保温1h，取样GC检测，当N-苯基对苯二胺含量不再降低时，停止反应，静置，分去水相，得到含中间体B31的三甲基环己烷溶液。
(3)化合物I-9的合成
向步骤(2)中得到的中间体B31的三甲基环己烷溶液中加入105g N-异丙基对苯二胺(0.7mol)，升温至100℃反应，用GC检测，当N-异丙基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和， 水洗后蒸馏三甲基环己烷，得到粗品。然后用石油醚重结晶，干燥后得到296.7g(收率85％)2-叔辛胺-4-(4-苯胺基苯胺)-6-(4-异丙胺基苯胺)-1,3,5-三嗪(化合物I-9)。
Figure PCTCN2020125100-appb-000021
化合物I-9的性状：紫褐色固体。
1H-HMR(400MHz,DMSO-D6,δppm)：8.47(q,2H),7.93(s,1H),7.6(s,2H),7.38(s,2H),7.17(t,2H),6.9(t,4H),6.77(t,1H),6.45(d,2H),6.14(d,1H),4.95(d,1H),3.29(m,1H),1.50(m,2H),1.41-1.31(m,12H),0.95(s,9H)。
实施例10：2-叔辛胺-4-(4-苯胺基苯胺)-6-(4-(1,4-二甲戊胺基)苯胺)-1,3,5-三嗪(化合物I-10)
(1)中间体A3的合成
称取118.1g三聚氯氰(0.64mol)溶于360g二甲苯中，加入71.2g碳酸钠固体粉末，在35℃剧烈搅拌条件下滴加86.5g叔辛胺的二甲苯溶液(0.67mol叔辛胺+80g二甲苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A3的无色透明溶液。
(2)中间体B31的合成
称取129.6g N-苯基对苯二胺(0.7mol)溶于180g二甲苯中，升温至80℃，剧烈搅拌下滴加步骤(1)中得到的中间体A3的二甲苯溶液，同时滴加157.6g氢氧化钾(25wt％)，滴加1～2h，保温1h，取样HPLC检测，当测不出中间体A3时，停止反应，水洗，得到含中间体B31的二甲苯溶液。
(3)化合物I-10的合成
向步骤(2)中得到的中间体B31的二甲苯溶液中加入131.9g N-1,4-二甲戊基对苯二胺(0.64mol)，升温至110℃反应，用GC检测，当N-1,4-二甲基戊基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，水洗后蒸馏二甲苯，得到粗品。然后用石油醚重结晶，干燥后得到288.9g(收率76％)2-叔辛胺-4-(4-苯胺基苯胺)-6-(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-10)。
Figure PCTCN2020125100-appb-000022
化合物I-10的性状：深紫色固体。
1H-NMR(400MHz,DMSO-D6,δppm):8.49(q,2H),7.91(s,1H),7.64(s,2H),7.34(s,2H),7.17(t,2H),6.98(t,4H),6.73(t,1H),6.48(d,2H),6.04(d,1H),4.95(d,1H),3.29(m,1H),1.89(s,1H),1.50(m,2H),1.40(s,6H),1.31-1.18(m,4H),1.07(d,3H),0.95(s,9H),0.86(q,6H)。
实施例11：2-叔辛胺-4-(4-异丙胺基苯胺)-6-(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-11)
(1)中间体A3的合成
称取118.1g三聚氯氰(0.64mol)溶于360g二甲苯中，加入71.2g碳酸钠固体粉末，在35℃剧烈搅拌条件下滴加86.5g叔辛胺的二甲苯溶液(0.67mol叔辛胺+80g二甲苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A3的无色透明溶液。
(2)中间体B32的合成
称取105g N-异丙基对苯二胺(0.7mol)溶于180g二甲苯中，升温至65℃，剧烈搅拌下滴加步骤(1)中得到的中间体A3的二甲苯溶液，同时滴加112.6g氢氧化钠溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当测不出中间体A3时，停止反应，静置，分去水相，得到含中间体B32的二甲苯溶液。
(3)化合物I-11的合成
向步骤(2)中得到的中间体B32的二甲苯溶液中加入144.2g N-1,4-二甲戊基对苯二胺(0.7mol)，升温至120℃反应，用GC检测，当N-1,4-二甲戊基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，有机相水洗后蒸馏二甲苯，得到粗品。然后用石油醚重结晶，干燥后得到286.7g(收率80％)2-叔辛胺-4-(4-异丙胺基苯胺)-6-(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-11)。
Figure PCTCN2020125100-appb-000023
化合物I-11的性状：紫褐色粘稠固体。
1H-HMR(400MHz,DMSO-D6,δppm)：8.32(d,2H),7.39(s,4H),6.49(d,4H),6.04(br,1H),4.99(t,3H),3.21-3.32(m,2H),1.36-1.15(m,15H),1.08-1.13(d,6H),1.02(s,9H),0.91(q,6H)。
实施例12：2-叔辛胺-4,6-二(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-12)
(1)中间体A3的合成
称取118.1g三聚氯氰(0.64mol)溶于360g二甲苯中，加入71.2g碳酸钠固体粉末，在25℃剧烈搅拌条件下滴加86.5g叔辛胺的二甲苯溶液(0.67mol叔辛胺+80g二甲苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测， 当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A3的无色透明溶液。
(2)中间体B33的合成
称取144.2g N-1,4-二甲戊基对苯二胺(0.7mol)溶于180g二甲苯中，升温至90℃，剧烈搅拌下滴加步骤(1)中得到的中间体A3的二甲苯溶液，同时滴加112.6g氢氧化钠溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当测不出中间体A3时，停止反应，静置，分去水相，得到含中间体B33的二甲苯溶液。
(3)化合物I-12的合成
向步骤(2)中得到的中间体B33的二甲苯溶液中加入152.4g N-1,4-二甲戊基对苯二胺(0.74mol)，升温至180℃反应，用GC检测，当N-1,4-二甲戊基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，有机相水洗后蒸馏二甲苯，得到粗品。然后用石油醚重结晶，干燥后得到295.6g(收率75％)2-叔辛胺-4,6-二(4-(1,4-二甲基戊胺基)苯胺)-1,3,5-三嗪(化合物I-12)。
Figure PCTCN2020125100-appb-000024
化合物I-12的性状：深紫色粘稠液体。
1H-NMR(400MHz,DMSO-D6,δppm)：8.30(d,2H),7.38(s,4H),6.51(d,4H),5.94(br,1H),4.99(d,2H),3.21-3.32(m,2H),1.91(s,2H),1.58-1.44(m,4H),1.38(s,6H),1.36-1.15(m,6H),1.08-1.13(d,6H),0.99(s,9H),0.91(q,12H)。
实施例13：2-环己胺-4,6-二(4-苯胺基苯胺)-1,3,5-三嗪(化合物I-13)
(1)中间体A4的合成
称取118.1g三聚氯氰(0.64mol)溶于360g甲苯中，加入71.2g碳酸钠固体粉末，在25℃剧烈搅拌条件下滴加66.4g环己胺的甲苯溶液(0.67mol环己胺+80g甲苯)，滴加1.5h，滴完后继续反应1.5h，取样进行GC检测，当检测不出三聚氯氰时，停止反应，过滤出固体，得到中间体A4的无色透明溶液。
(2)中间体B43的合成
称取128.8g N-苯基对苯二胺(0.7mol)溶于180g甲苯中，升温至100℃，剧烈搅拌下滴加步骤(1)中得到的中间体A4的甲苯溶液，同时滴加112.6g氢氧化钠溶液(25wt％)，滴加1～2h，保温1h，取样GC检测，当测不出中间体A4时，停止反应，静置，分去水相，得到含中间体B43的甲苯溶液。
(3)化合物I-13的合成
向步骤(2)中得到的中间体B43的甲苯溶液中再加入132.5g N-苯基对苯二胺(0.72mol)，升温至140℃反应，用GC检测，当N-苯基对苯二胺含量不再降低时，降温，停止反应，加入112.6g氢氧化钠溶液(25wt％)中和，有机相水洗后蒸馏甲苯，得到粗品。然后用石油醚重结晶，干燥后得到277.5g(收率80％)2-环己胺-4,6-二(4-苯胺基苯胺)-1,3-5-三嗪(化合物I-13)。
Figure PCTCN2020125100-appb-000025
化合物I-13的性状：深褐色固体。
1H-NMR(400MHz,DMSO-D6,δppm)：8.63(s,2H)，7.82(s,2H)，7.64(br,4H)，7.19(t,4H)，6.89(q,8H)，6.65(t,2H)，6.21(s,1H)，3.2-3.4(m,5H)，2.41(br,6H)。
测试例：
根据表1所示的配方制备测试例1-6的橡胶组合物，具体包含如下步骤：
1、向密炼机中加入天然橡胶SCR5和合成胶BR，捏合一段时间后，加入炭黑N550、芳烃油、氧化锌、硬脂酸和防老剂(6PPD、化合物I-5、化合物 I-3、化合物I-6、化合物I-10或化合物I-12)，继续捏合直至混合均匀；捏合期间温度控制在150℃和160℃之间；
2、将整个混合物冷却至100℃以下，然后加入交联体系(硫磺S和促进剂NS)，捏合整个混合物；捏合期间控制温度不超过110℃；
3、将所得的橡胶组合物压延为片状(厚度为2-3mm)，进行硫化，硫化温度为145℃，时间为30分钟。
表1中各成分的来源如下：
SCR5：西双版纳中化橡胶有限公司天然胶SCR5；
BR：南京扬子石化橡胶有限公司合成胶BR9000；
N550：卡博特公司炭黑N550；
芳烃油：上海泰坦科技股份有限公司通用试剂；
硬脂酸：上海泰坦科技股份有限公司通用试剂硬脂酸(AR)；
氧化锌：上海泰坦科技股份有限公司通用试剂氧化锌(AR)；
NS：圣奥化学科技有限公司硫化促进剂NS；
S：国药集团化学试剂公司升华硫(AR)；
6PPD：圣奥化学科技有限公司防老剂SIRANTOX 6PPD；
化合物I-5：实施例5合成的化合物；
化合物I-3：实施例3合成的化合物；
化合物I-6：实施例6合成的化合物；
化合物I-10：实施例10合成的化合物；
化合物I-12：实施例12合成的化合物。
表1：橡胶组合物的配方(单位：质量份)
配方 测试例1 测试例2 测试例3 测试例4 测试例5 测试例6
SCR5 50.0 50.0 50.0 50.0 50.0 50.0
BR 50.0 50.0 50.0 50.0 50.0 50.0
N550 50.0 50.0 50.0 50.0 50.0 50.0
芳烃油 5.0 5.0 5.0 5.0 5.0 5.0
氧化锌 5.0 5.0 5.0 5.0 5.0 5.0
硬脂酸 2.0 2.0 2.0 2.0 2.0 2.0
6PPD 2.5          
化合物I-5   2.5        
化合物I-3     2.5      
化合物I-6       2.5    
化合物I-10         2.5  
化合物I-12           2.5
NS 0.8 0.8 0.8 0.8 0.8 0.8
S 1.5 1.5 1.5 1.5 1.5 1.5
合计 166.8 166.8 166.8 166.8 166.8 166.8
按照以下的方法评估测试例1-6的硫化橡胶片的抗臭氧性能和耐变色性能，结果如表3所示。
(1)抗臭氧性能评估方法
在温度为40℃，臭氧浓度为50pphm，且伸长率为20％的条件下，将各种橡胶组合物的试验片进行臭氧劣化试验。经39小时后，检查该试验片的劣化状态。抗臭氧性能等级基于形成的裂缝密度，其评判标准为：
0：没有裂纹
1：少量裂纹(裂纹密度＜10条/cm)
2：较多裂纹(10条/cm≤裂纹密度＜40条/cm)
3：大量裂纹(裂纹密度≥40条/cm)
(2)耐变色性能评估方法
将硫化胶片装入自封袋中，使胶片紧贴袋子，在室外条件暴露两周后观察袋子颜色变化。耐变色性能等级的评判标准如表2所示。
表2：变色等级说明
等级 描述
0 无变色
1 少面积轻微变色，需要仔细对比才能发现
2 较大面积或全部轻微变色，对比后容易发现
3 少面积严重变色，能直接发现
4 较大面积或全部严重变色，能直接发现
表3：橡胶耐臭氧和耐变色实验结果
Figure PCTCN2020125100-appb-000026
由表1和表2可知，相比于含有常规防老剂的橡胶组合物，含有本发明化合物的胶料耐臭氧性相同或者更好，而且含有本发明化合物的胶料变色明显受到抑制。

Claims (10)

  1. 下式(I)所示的化合物：
    Figure PCTCN2020125100-appb-100001
    其中，
    R为C3～C16烷基、C3～C10环烷基取代的C3～C16烷基、C3～C10环烷基或C3～C16烷基取代的C3～C10环烷基；
    R 1和R 2相同或不同，各自独立选自C3～C10烷基、C3～C10环烷基或C6～C14芳基取代的C3～C10烷基、C3～C10环烷基、C3～C10烷基取代的C3～C10环烷基、C6～C14芳基和C3～C10烷基取代的C6～C14芳基。
  2. 如权利要求1所述的化合物，其特征在于，R为C3～C10烷基或C3～C10环烷基，优选为C3～C10支链烷基或C3～C10环烷基，更优选为异丙基、叔丁基、叔辛基或环己基。
  3. 如权利要求1所述的化合物，其特征在于，R 1和R 2相同或不同，各自独立为C3～C10烷基或苯基，优选各自独立为C3～C10支链烷基或苯基，更优选各自独立为异丙基、1,4-二甲基戊基或苯基。
  4. 如权利要求1所述的化合物，其特征在于，所述化合物选自：
    Figure PCTCN2020125100-appb-100002
    Figure PCTCN2020125100-appb-100003
    Figure PCTCN2020125100-appb-100004
    Figure PCTCN2020125100-appb-100005
  5. 一种制备权利要求1-4中任一项所述的化合物的方法，其特征在于，所述方法包括：
    (1)使三聚氯氰与NH 2R反应，制备得到下式所示的中间体A：
    Figure PCTCN2020125100-appb-100006
    (2)使中间体A与N-R 1-对苯二胺反应，制备得到下式所示的中间体B：
    Figure PCTCN2020125100-appb-100007
    (3)使中间体B与N-R 2-对苯二胺反应，制备得到式(I)化合物：
    Figure PCTCN2020125100-appb-100008
    其中，中间体A、中间体B和式(I)化合物中的R、R 1和R 2如权利要求1-4中任一项所定义。
  6. 如权利要求5所述的方法，其特征在于，所述方法具有以下一项或多项特征：
    (A)步骤(1)的反应中添加碱性固体粉末，反应温度为0～35℃；
    (B)步骤(2)的反应中添加碱液，反应温度为50～100℃；和
    (C)步骤(3)的反应温度为80～180℃。
  7. 如权利要求5所述的方法，其特征在于，R 1和R 2相同，所述步骤(2)和步骤(3)合并为步骤(2’)：使中间体A和N-R 1-对苯二胺反应，制备得到式(I)化合物；
    优选地，步骤(1)的反应中添加碱性固体粉末，反应温度为0～35℃；
    优选地，步骤(2’)的反应中添加碱液，反应先在50～100℃下进行，然后在80～180℃下进行。
  8. 一种橡胶组合物，所述橡胶组合物含有权利要求1-4中任一项所述的化合物。
  9. 一种橡胶制品，所述橡胶制品采用权利要求8所述的橡胶组合物作为橡胶组分制备得到；优选地，所述橡胶制品为轮胎。
  10. 权利要求1-4中任一项所述的化合物在提高橡胶或橡胶制品的抗老化性能和/或耐变色性能中的用途；优选地，所述橡胶制品为轮胎。
PCT/CN2020/125100 2019-11-04 2020-10-30 具有抗老化和耐变色功效的化合物及其制备方法 WO2021088721A1 (zh)

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