Aromatic amine compound as well as preparation method and application thereof

Abstract

The invention discloses an aromatic amine compound and a preparation method and application thereof.The aromatic amine compound is large in molecular weight, not prone to migration to the surface when used in rubber and other products, good in compatibility with rubber, not prone to blooming, good in anti-aging effect and capable of achieving the same or even better anti-aging effect compared with an existing anti-aging agent product, and the aromatic amine compound has the good anti-aging effect. The product can be used as an industrial anti-aging agent and a plasticizer.

Description

Technical Field

[0001] The present invention relates to a new type of aromatic amine compounds, in particular to a type of aromatic amine compounds derived from phenylamine groups, a preparation method of the compounds, and application of the compounds as industrial antioxidants and / or plasticizers. Background Art

[0002] At present, p-phenylenediamine compounds are commonly used as antioxidants in rubber products, especially tires. This type of antioxidant is a high-efficiency, multi-functional, low-toxic, and long-lasting antioxidant product. It is the most important and most widely used type of antioxidant. It can be used in rubber, plastic, engine oil, lubricating oil, heat transfer oil, diesel, gasoline, adhesives and other products to prevent, stop and slow down the aging and degradation of the above products due to heat, oxygen (such as O2, O3, etc.), flexing (for rubber, plastic, plastic), harmful metals (such as copper and manganese, etc.). Its main use is in the rubber industry. The p-phenylenediamine antioxidants specifically include dialkyl p-phenylenediamine, alkylaryl p-phenylenediamine and diaryl p-phenylenediamine. The most widely used antioxidant is 4020 (N-(1,3-dimethylbutyl)-N′-phenyl p-phenylenediamine). Others include IPPD (N-isopropyl-N′-phenyl p-phenylenediamine), 77PD (N,N′-bis(1,4-dimethylpentyl) p-phenylenediamine), DTPD (a mixture of diphenyl p-phenylenediamine, di(tolyl) p-phenylenediamine and phenyltolyl p-phenylenediamine), etc.

[0003] The molecular weight of antioxidant 4020 is relatively small, and during the use of rubber products or tires, the antioxidant can easily migrate to the surface, causing pollution and discoloration of the tire surface; the antioxidant DTPD is a diaryl-p-phenylenediamine, which is a recognized long-lasting and after-effect antioxidant with relatively long-lasting anti-aging performance, but has poor compatibility with rubber, and large dosage leads to frosting. In recent years, users have paid more and more attention to the anti-aging durability and surface discoloration of tires. Therefore, the field urgently needs an antioxidant product that has a longer-lasting aging protection effect and is resistant to discoloration than existing products. Summary of the invention

[0004] In view of the problems of easy discoloration and blooming of current antioxidant products such as 6PPD, which leads to reduced anti-aging effect and poor durability, the present invention provides an aromatic amine compound, which has a large molecular weight and is not easy to migrate to the surface when used in products such as rubber, and has good compatibility with rubber and is not easy to bloom. The compound has a good anti-aging effect and can achieve the same or even better anti-aging effect as existing antioxidant products.

[0005] The present invention provides an aromatic amine compound having a structural formula shown in the following formula (I):

[0006]

[0007] Furthermore, in formula (I), the substituent R is a C1-C10 alkyl or cyclohexyl group, such as methyl, ethyl, isopropyl, 1-methylheptyl, 1-methylhexyl, 1,3-dimethylbutyl, cyclohexyl, 1,4-dimethylpentyl, and the like.

[0008] Furthermore, the aromatic amine compound is one of the compounds of the following structural formulas:

[0009]

[0010]

[0011] The present invention also provides a method for preparing the above aromatic amine compounds, which comprises the following steps:

[0012] S1. Preparation of intermediate: 4,4-dinitrodiphenylamine and p-chloronitrobenzene are reacted under the action of catalyst 1 to obtain an intermediate; the reaction equation is as follows:

[0013]

[0014] S2: preparing aromatic amine compounds: subjecting the intermediate prepared in step S1 and the ketone to a catalytic hydrogenation reaction under the action of hydrogen and catalyst 2 to obtain aromatic amine compounds represented by formula (I); the reaction equation is as follows:

[0015]

[0016] Further, in step S1, the catalyst 1 used in the reaction is a mixture of a carbonate catalyst and a copper catalyst. The carbonate catalyst is one of sodium bicarbonate, sodium carbonate, and potassium carbonate. The copper catalyst is one of copper oxide, cuprous oxide, and skeleton copper.

[0017] Preferably, the carbonate catalyst is potassium carbonate, and the copper catalyst is copper oxide.

[0018] Furthermore, in step S1, the molar ratio of p-chloronitrobenzene to the carbonate catalyst is 1:1.1-1.5, for example, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5.

[0019] Furthermore, in step S1, the copper catalyst is 0.5-1% of the mass of 4,4-dinitrodiphenylamine, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.

[0020] Furthermore, in step S1, the molar ratio of 4,4-dinitrodiphenylamine to p-chloronitrobenzene is 1.01-1.05:1, for example, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05.

[0021] Furthermore, in step S1, an acid binding agent such as sodium hydroxide may be added to remove the hydrogen chloride formed during the reaction.

[0022] Further, in step S1, the reaction is carried out in an organic solvent, and the organic solvent can be selected from the solvents disclosed in the prior art as a reaction medium, such as acetonitrile, toluene, dimethyl sulfoxide, acetylacetone, etc. The amount of the organic solvent can be adjusted and selected according to actual needs. Among them, the raw material has better solubility in dimethyl sulfoxide, so the organic solvent is preferably dimethyl sulfoxide.

[0023] Further, in step S1, the reaction temperature is controlled to reflux the reaction liquid, that is, heated to reflux for reaction. The intermediate preparation process of the present invention is fast, and the reaction can be completed in about 20 minutes at the reflux temperature, generally 10-30 minutes, for example 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, 21 minutes, 22 minutes, 23 minutes, 24 minutes, 25 minutes, 26 minutes, 27 minutes, 28 minutes, 29 minutes, 30 minutes.

[0024] Furthermore, in step S1, after the reaction is completed, the reaction solution is filtered to remove the catalyst 1 while it is hot, and then the organic solvent is removed under reduced pressure to obtain an intermediate.

[0025] Further, in step S2, the ketone includes acetone, 2-octanone, heptanone, methyl isobutyl ketone, methyl isobutyl ketone, cyclohexanone, methyl isoamyl ketone, etc.

[0026] Furthermore, in step S2, the added ketone is both a raw material and a reaction solvent, and no other solvent is added in this step of the reaction. The molar ratio of the intermediate to the ketone is 1:4-8, for example, 1:4, 1:5, 1:6, 1:7, 1:8.

[0027] Further, in step S2, the catalyst 2 is at least one of a palladium catalyst, a nickel catalyst, a copper catalyst, a copper-zinc-aluminum-nickel catalyst, and a copper-zinc-aluminum-chromium catalyst. Wherein, the palladium catalyst includes a palladium-carbon catalyst, the nickel catalyst includes a carbon-based nickel catalyst, the copper catalyst includes a carbon-based copper catalyst, the copper-zinc-aluminum-nickel catalyst includes a composite composition of copper oxide, zinc oxide, aluminum oxide, and nickel oxide, and the copper-zinc-aluminum-chromium catalyst includes a composite composition of copper oxide, zinc oxide, aluminum oxide, and chromium oxide. Wherein, palladium-carbon is formed by loading metal palladium into activated carbon. Carbon-based nickel is a molecular crystal, called tetracarbonyl nickel. Carbon-based copper is a Cu-N / C single atom catalyst.

[0028] Preferably, the catalyst 2 is a palladium catalyst, more preferably a palladium-carbon catalyst, and the loading amount of palladium is 2-5wt%.

[0029] Furthermore, in step S2, the amount of catalyst 2 used is 2-6% of the mass of the intermediate, for example, 2%, 3%, 4%, 5%, 6%.

[0030] Furthermore, in step S2, hydrogen is continuously added during the reaction to maintain the hydrogen pressure at 1.5-2.0 MPa until the reaction is completed.

[0031] Further, in step S2, the reaction temperature is 81-85°C, for example, 81°C, 82°C, 83°C, 84°C, 85°C.

[0032] Furthermore, in step S2, after the reaction is completed, the catalyst 2 is filtered out of the reaction solution, and the excess ketone and the generated alcohol are removed by reduced pressure distillation to obtain the aromatic amine compound product of the present invention.

[0033] The aromatic amine compounds of the present invention have many amine active groups, large molecular weight, are not easy to migrate out, are not easy to bloom, and have good anti-discoloration performance. They can be used as antioxidants and / or plasticizers, especially as rubber antioxidants, for preparing rubber products or tires.

[0034] The invention also provides a rubber antioxidant mixture, which comprises the aromatic amine compound.

[0035] The present invention also provides a rubber composition, which comprises the aromatic amine compound.

[0036] The present invention also provides a rubber product, which comprises the rubber composition; preferably, the rubber product is a tire.

[0037] The present invention also provides a method for improving the heat-oxidative aging resistance of rubber and / or rubber products, which comprises adding the aromatic amine compound or antioxidant mixture into the rubber and / or rubber products.

[0038] The present invention has the following beneficial effects:

[0039] 1. Compared with diaryl-p-phenylenediamine and arylalkyl-p-phenylenediamine antioxidants, the aromatic amine compounds of the present invention have more amine groups, larger molecular weight, and are not easy to migrate out. They can significantly improve the tire side discoloration phenomenon caused by traditional p-phenylenediamine antioxidants, effectively solve the "frosting" phenomenon caused by the easy migration of organic antioxidants, have a more lasting anti-aging effect, and have a higher application value in the anti-aging of rubber materials.

[0040] 2. The preparation process of aromatic amine compounds is simple, the product yield is high, the product quality is stable, and it is suitable for industrial application.

[0041] 3. The aromatic amine compounds of the present invention can achieve the same or even higher anti-aging effect as the traditional p-phenylenediamine antioxidants, can be used as industrial antioxidants and plasticizers, and are a very promising antioxidant 4020 alternative antioxidant. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 The following is the H NMR spectrum of the product obtained in Example 1.

[0043] Figure 2 The carbon-NMR spectrum of the product obtained in Example 1 is shown in FIG.

[0044] Figure 3 This is the H NMR spectrum of the product obtained in Example 2.

[0045] Figure 4 The carbon-NMR spectrum of the product obtained in Example 2 is shown in FIG.

[0046] Figure 5 The following is the H NMR spectrum of the product obtained in Example 3.

[0047] Figure 6 The following is the NMR carbon spectrum of the product obtained in Example 3.

[0048] Figure 7 This is the result of the dynamic ozone color change experiment. DETAILED DESCRIPTION

[0049] The present invention will be further described in detail below in conjunction with specific examples to make the advantages of the present invention more obvious. It should be understood that the contents thereof are only used for illustration and are by no means intended to limit the scope of protection of the present invention. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0050] Unless otherwise specified, the following concentrations are all mass percentages.

[0051] In the following examples, the copper oxide and palladium carbon catalyst used were purchased from MacLean.

[0052] Example 1

[0053] S1: Preparation of intermediates:

[0054] Weigh 600g of solvent dimethyl sulfoxide, 262.81g (1.01mol) of 4,4-dinitrodiphenylamine, 157g (1mol) of p-chloronitrobenzene, 40g (1mol) of sodium hydroxide, 152.03g (1.1mol) of potassium carbonate, and 2.1g of copper oxide, add them into a suitable three-necked flask, stir, and heat to reflux in an oil bath pot, reflux for 20-30min, and the reaction is complete when the residual amount of 4,4-dinitrodiphenylamine is less than 0.1% (HPLC). After filtering the catalyst from the reaction solution while it is hot, remove the solvent under reduced pressure to obtain 370.3g of the intermediate, with a yield of 97.4% based on p-chloronitrobenzene.

[0055] S2: Synthesis of aromatic amine compounds:

[0056] Weigh 190.16g (0.5mol) of the intermediate, 145.2g (2.5mol) of acetone, and 3.8g of palladium-carbon catalyst, add them into an autoclave, replace with nitrogen three times to ensure that there is no oxygen in the autoclave, heat it to 85°C, fill it with hydrogen at 1.5-2.0MPa and keep it constant, and continuously add hydrogen during the reaction until the reaction no longer consumes hydrogen and the intermediate content is less than 0.1% (HPLC), then the reaction is complete. Filter the synthetic liquid, and distill under reduced pressure to remove the remaining acetone and the generated alcohol to obtain 200.13g of the product of the present invention, with a yield of 96.1% based on the intermediate and a purity of 96.41% (HPLC).

[0057] The obtained product structure is: Its H NMR spectrum and C NMR spectrum are as follows Figure 1 and 2 shown.

[0058] Example 2

[0059] S1: Preparation of intermediates:

[0060] Weigh 600g of solvent dimethyl sulfoxide, 262.81g (1.01mol) of 4,4-dinitrodiphenyl, 157g (1mol) of p-chloronitrobenzene, 165.84g (1.2mol) of potassium carbonate, 40g (1mol) of sodium hydroxide, and 1.49g of copper oxide, add them into a suitable three-necked flask, then stir, and heat to reflux in an oil bath pot, reflux for about 20-30min, and the remaining amount of 4,4-dinitrodiphenylamine is less than 0.1% (HPLC), then the reaction is complete. Filter the reaction solution while hot, remove the solvent under reduced pressure, and obtain 369.89g of the intermediate, with a yield of 97.3% based on p-chloronitrobenzene.

[0061] S2: Synthesis of aromatic amine compounds:

[0062] Weigh 190.16g (0.5mol) of intermediate, 384.64g (3mol) of 2-octanone, and 3.8g of palladium-carbon catalyst, add them into an autoclave, replace with nitrogen three times to ensure that there is no oxygen in the autoclave, heat to 85°C, charge with 1.5-2.0MPa of hydrogen and keep it unchanged, and continuously add hydrogen during the reaction until the reaction no longer consumes hydrogen and the intermediate content is less than 0.1% (HPLC), then the reaction is complete. Filter the synthetic liquid, and distill under reduced pressure to remove the remaining 2-octanone and the generated alcohol to obtain 303.24g of the product of the present invention, with a yield of 96.7% based on the intermediate and a purity of 96.24% (HPLC).

[0063] The obtained product structure is: Its H NMR spectrum and C NMR spectrum are as follows Figure 3 and 4 shown.

[0064] Example 3

[0065] S1: Preparation of intermediates:

[0066] Weigh 600g of solvent dimethyl sulfoxide, 262.81g (1.01mol) of 4,4-dinitrodiphenyl, 157g (1mol) of p-chloronitrobenzene, 127.2g (1.2mol) of sodium carbonate, 40g (1mol) of sodium hydroxide, and 2.1g of copper oxide, add them into a suitable three-necked flask, stir, and heat to reflux in an oil bath pot, reflux for about 20-30min, and the remaining amount of 4,4-dinitrodiphenylamine is less than 0.1% (HPLC), then the reaction is complete. Filter the reaction solution while hot, remove the solvent under reduced pressure, and obtain 369.5g of the intermediate, with a yield of 97.2% based on p-chloronitrobenzene.

[0067] S2: Synthesis of aromatic amine compounds:

[0068] Weigh 190.16g (0.5mol) of intermediate, 294.42g (3mol) of pimelinketone, 3.8g of palladium-carbon catalyst (loading capacity 3%), add to autoclave, replace with nitrogen 3 times, ensure that there is no oxygen in the autoclave, heat to 85°C, charge with 1.5-2.0MPa of hydrogen and keep unchanged, and continuously add hydrogen during reaction until the reaction no longer consumes hydrogen and the intermediate content is lower than 0.1% (HPLC), then the reaction is complete. Filter the synthetic liquid, distill under reduced pressure to remove the remaining pimelinketone and the generated alcohol, and obtain 263.57g of product of the present invention, with the yield of 98.2% based on the intermediate and the purity (HPLC) being 97.87%.

[0069] The obtained product structure is: Its H NMR spectrum and C NMR spectrum are as follows Figure 5 and 6shown.

[0070] Example 4

[0071] S1: Preparation of intermediate: same as Example 2.

[0072] S2: Synthesis of aromatic amine compounds:

[0073] Weigh 190.16g (0.5mol) of intermediate, 300.48g (3mol) of methyl isobutyl ketone, 3.8g of palladium carbon catalyst (loading 3%), add them into an autoclave, replace with nitrogen 3 times to ensure that there is no oxygen in the autoclave, heat to 87°C, charge with 1.5-2.0MPa of hydrogen and keep it unchanged, and continuously add hydrogen during the reaction until the reaction no longer consumes hydrogen and the intermediate content is less than 0.1% (HPLC), then the reaction is complete. Filter the synthetic liquid, distill under reduced pressure to remove the remaining methyl isobutyl ketone and the generated alcohol, and obtain 264.37g of the product of the present invention, with a yield of 97.4% based on the intermediate and a purity (HPLC) of 98.65%.

[0074] The obtained product structure is: Comparative Example 1

[0075] In the S1 intermediate synthesis step, copper oxide was not added, and the remaining operation steps were exactly the same as those in Example 1, and ultimately no intermediate was obtained.

[0076] Comparative Example 2

[0077] In the S1 intermediate synthesis step, potassium carbonate was not added, and the remaining operation steps were exactly the same as those in Example 1. The content of the intermediate in the final reaction solution was 0.4%, and almost no intermediate was obtained.

[0078] Performance Verification

[0079] 1. Rubber compound formula and rubber compound preparation

[0080] Rubber formula (weight parts): natural rubber NR 45 parts, butadiene rubber BR 55 parts, carbon black N330 45 parts, zinc oxide ZnO-80 4.375 parts, stearic acid SA 2 parts, protective wax H3241 1.8 parts, vulcanizing agent S-80

[0081] 1.875 parts, accelerator NS-80 1 part, antioxidant 3 parts. The antioxidants are aromatic amine compounds and antioxidant 4020 prepared in each example, and the rubber material without antioxidant is used as a blank control.

[0082] The preparation of rubber can be divided into a one-stage mixing process and a two-stage mixing process. The specific one-stage mixing process is as follows: weigh the raw materials according to the formula ratio, and mix 45 parts of natural rubber NR, 55 parts of butadiene rubber BR, 45 parts of carbon black N330, 4.375 parts of zinc oxide ZnO-80, 2 parts of stearic acid SA, and protective wax H3241 1.8 parts of sulfoxide and 3 parts of antioxidant are added to the internal mixer, the rotor speed is 60-70 rpm, the pressure is 19-20MPa, the heating rate is 5-10℃ / 10 minutes, the temperature is raised to 100-120℃, the temperature is kept for 5-10 minutes, and the temperature is further raised to 180℃, and the rubber is discharged to obtain the first-stage mixed rubber; the second-stage mixing process is specifically as follows: the first-stage mixed rubber is added to the internal mixer, the vulcanizing agent S-80 and the accelerator NS-80 are added and mixed, and the pressure is 8-10MPa, the temperature is 70-80℃, and the mixing is carried out for 1-2 minutes at a speed of 10-15 rpm. After completion, the rubber compound can be obtained.

[0083] 2. Test methods for various performance parameters of rubber materials

[0084] Processing performance test: Using Mooney viscometer, scorch test was carried out according to the national standard GB / T 1233-92.

[0085] Vulcanization property test: P3555 B2 disc vulcanizer produced by Beijing Huanfeng Rubber & Plastic Machinery Manufacturing Factory was used for testing according to GB / T 98691997, with a test temperature of 160°C and a test time of 60 min.

[0086] Mechanical properties test: CMT 4104 electronic tensile testing machine produced by Shenzhen Xinsansi Material Testing Co., Ltd. was used to measure the tensile properties of the vulcanized rubber according to GB / T 528-2009; according to GB / T 77591996, a 29.0mm×12.5mm cylindrical specimen was used to measure the compression permanent deformation at 100℃×72h, with a pre-compression rate of 25%.

[0087] Ozone resistance test: Ozone resistance test is carried out according to GB / T 13642-2015 "Dynamic tensile test of vulcanized rubber or thermoplastic rubber for ozone cracking resistance".

[0088] 3. Experimental results

[0089] The processing characteristics of the rubber are shown in Table 1 below:

[0090] Table 1 Processing characteristics of rubber compounds

[0091] Rubber t5 / min Mn / Mv Blank control 30.34 63.50 Antioxidant 4020 28.33 47.01 Example 1 28.45 47.86 Example 2 28.57 47.23 Example 3 28.54 47.56 Example 4 28.61 47.81

[0092] It can be seen from Table 1 that, compared with the blank control, the addition of the products of each embodiment of the present invention shortens the scorch time of the mixed rubber, reduces the Mooney viscosity, and improves the processing performance; compared with the antioxidant 4020 product, the products of each embodiment of the present invention have similar processing performance and equivalent processing safety to the antioxidant 4020.

[0093] The vulcanization characteristics of the rubber are shown in Table 2 below:

[0094] Table 2 Vulcanization characteristics of rubber compounds

[0095]

[0096]

[0097] It can be seen from Table 2 that, compared with the blank sample without adding the antioxidant, the addition of the products of each embodiment of the present invention improves the vulcanization rate and the degree of vulcanization crosslinking of the mixed rubber, and the effect is better than that of the antioxidant 4020.

[0098] The mechanical properties of the rubber are shown in Table 3 and Table 4:

[0099] Table 3 Mechanical properties before aging test

[0100]

[0101] Table 4 Mechanical properties after aging test

[0102]

[0103] It can be seen from Table 3 and Table 4 that before the aging experiment, compared with the blank control, after adding antioxidant 4020 or the antioxidant products of each embodiment of the present invention to the rubber material, the tensile strength and tensile stress of the vulcanized rubber were improved. After the aging experiment, the products of each embodiment of the present invention have better resistance to thermal oxidative aging.

[0104] Figure 7 The figures are the results of the dynamic ozone aging discoloration experiment, among which No. 3 is the blank control group, No. 4 is the protective effect of 4020, No. 1, No. 2, No. 5, and No. 6 are the protective effects of Example 1, Example 2, Example 3, and Example 4. It can be seen from the figure that the high molecular weight antioxidant provided by the present invention is significantly better than the protective effect of 4020.

[0105] In summary, the novel antioxidant with high molecular weight provided by the present invention not only has excellent ozone protection effect, but also can effectively solve the problem of easy migration and discoloration of organic antioxidants, and has high potential application value in the anti-aging of rubber materials.

[0106] The above description is only a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been presented as a preferred embodiment as above, it is not intended to limit the present invention. Any technician familiar with the profession can make some changes or modifications to the equivalent embodiments of the same variations using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. An aromatic amine compound, characterized in that: It has the structural formula shown in the following formula (I): Wherein, R is a C1-C10 alkyl group or a cyclohexyl group.

2. A method for preparing the aromatic amine compound according to claim 1, characterized in that The following steps are involved: S1. reacting 4,4-dinitrodiphenylamine and p-chloronitrobenzene under the action of catalyst 1 to obtain an intermediate; S2. The intermediate prepared in S1 and the ketone are subjected to a catalytic hydrogenation reaction under the action of hydrogen and catalyst 2 to obtain an aromatic amine compound represented by formula (I).

3. The preparation method according to claim 2, characterized in that: In step S1, at least one of the following conditions is included: Condition 1: the catalyst 1 is a mixture of a carbonate catalyst and a copper catalyst; Condition 2: the molar ratio of 4,4-dinitrodiphenylamine to p-chloronitrobenzene is 1.01-1.05:1; Condition 3: The reaction is carried out in an organic solvent; Condition 4: During the reaction, the mixture is heated to reflux for reaction.

4. The preparation method according to claim 3, characterized in that: In step S1, the carbonate catalyst is selected from sodium bicarbonate, sodium carbonate or potassium carbonate, and the copper catalyst is selected from copper oxide, cuprous oxide or skeleton copper; preferably, the molar ratio of p-chloronitrobenzene to the carbonate catalyst is 1:1.1-1.5; preferably, the copper catalyst is 0.5-1% of the mass of 4,4-dinitrodiphenylamine.

5. The preparation method according to any one of claims 2 to 8, characterized in that: In step S2, at least one of the following conditions is included: Condition 1: The ketone includes acetone, 2-octanone, heptanone, methyl isobutyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl isoamyl ketone; Condition 2: The molar ratio of the intermediate to the ketone is 1:4-8; Condition 3: The catalyst 2 is at least one of a palladium catalyst, a nickel catalyst, a copper catalyst, a copper-zinc-aluminum-nickel catalyst, and a copper-zinc-aluminum-chromium catalyst, preferably a palladium catalyst; Condition 4: The amount of the catalyst 2 is 2-6% of the mass of the intermediate; Condition 5: During the reaction, hydrogen is continuously added to maintain the hydrogen pressure at 1.5-2.0 MPa until the reaction is completed; Condition 6: The reaction temperature is 81-85°C.

6. Use of the aromatic amine compound according to claim 1 as an antioxidant and / or a plasticizer.

7. An antioxidant mixture, characterized in that: Including the aromatic amine compound according to claim 1.

8. A rubber composition, characterized in that: Including the aromatic amine compound according to claim 1.

9. A rubber product, characterized in that: Comprising the rubber composition according to claim 8; preferably, the rubber product is a tire.

10. A method for improving the thermal oxygen aging resistance of rubber and / or rubber products, characterized in that: Add the aromatic amine compound described in claim 1 or the antioxidant mixture described in claim 7 to rubber and / or rubber products.

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