Compound, preparation method and application thereof, and rubber

Abstract

The invention relates to the field of rubber anti-aging agents, and discloses a compound, a preparation method and application thereof and rubber. Wherein the compound contains a cross-linked structure M and one or more structures A1 as shown in a formula (1) or structures A2 as shown in a formula (2) connected to the cross-linked structure M, and # imgabs0, R1 is selected from H or # imgabs1 #, R3 is selected from H or C1-C6 alkyl, R2 is selected from H or C1-C6 alkyl, R'does not exist or R 'is selected from C1-C20 oxygen-containing groups, and R' 'is selected from C1-C20 oxygen-containing groups; wherein the cross-linked structure M is selected from residues from tetraethoxysilane, 3-glycidyl ether oxypropyl trimethoxy silane or melamine, and the cross-linked structure M is selected from residues from tetraethoxysilane, 3-glycidyl ether oxypropyl trimethoxy silane or melamine. The compound has the protection performance of a traditional anti-aging agent and also has the characteristic of migration resistance; the preparation method of the compound only needs simple separation and purification, and has the advantages of simple process, high product yield and the like; in addition, the compound has good dispersity in rubber, and the use amount of a dispersing agent and other rubber additives required by rubber mixing can be reduced.

Description

Technical Field

[0001] The invention relates to the field of rubber antioxidants, and in particular to a compound, a preparation method and application thereof, and rubber. Background Art

[0002] Rubber materials are widely used in production and life due to their advantages of light weight, good flexibility, good sealing, and shock absorption and buffering. However, the unsaturated bonds in rubber materials can easily cause rubber aging, thus affecting the long-term use of rubber materials.

[0003] Rubber antioxidants are mainly divided into amine antioxidants, phenolic antioxidants, heterocyclic antioxidants and other categories, among which amine antioxidants are mostly small molecule compounds, such as IPPD, 6PPD, etc. Literature reports that the small molecule antioxidant 6PPD in automobile tires is easy to migrate out and will be further ozonated to form highly toxic substances, which has caused a sharp decline in the salmon population to a large extent. However, due to the small molecular weight of existing small molecule antioxidants, they are easy to volatilize, easy to migrate, and have poor extraction resistance during processing and use, resulting in a reduction in the concentration of antioxidants in rubber products. The anti-aging protection of rubber is not utilized, and the volatilized antioxidants will also cause harm to the environment and human health. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of the prior art that the rubber antioxidant is easy to volatilize, easy to migrate, has poor dispersibility in rubber and poor extraction resistance, and to provide a compound and its preparation method and application as well as rubber.

[0005] In order to achieve the above object, the present invention provides a compound in a first aspect, wherein the compound comprises a cross-linked structure M and one or more structures A1 represented by formula (1) or structures A2 represented by formula (2) connected to the cross-linked structure M.

[0006]

[0007] Wherein, R1 is selected from H or R3 is selected from H or C1-C6 alkyl, R2 is selected from H or C1-C6 alkyl, R' is absent or R' is selected from C1-C 20 Oxygen-containing group, R" is selected from C1-C 20 Oxygen-containing groups;

[0008] The cross-linked structure M is selected from residues of tetraethyl orthosilicate, 3-glycidyloxypropyltrimethoxysilane or melamine.

[0009] The second aspect of the present invention provides a method for preparing a compound, which comprises the following steps:

[0010] (1) subjecting an aniline compound to an addition reaction with an epoxy compound to obtain an intermediate product;

[0011] (2) in the presence of a catalyst, subjecting the intermediate product to a cross-linking reaction with a cross-linking agent to obtain the compound, wherein the cross-linking agent is a compound that does not contain an epoxy group;

[0012] Or include the following steps:

[0013] The compound is obtained by performing an addition cross-linking reaction between an aniline compound and a cross-linking agent, wherein the cross-linking agent is a compound containing an epoxy group.

[0014] The third aspect of the present invention provides a compound obtained by the preparation method.

[0015] The fourth aspect of the present invention provides a use of the compound as an antioxidant in rubber.

[0016] A fifth aspect of the present invention provides a rubber, wherein the rubber comprises raw rubber and the compound.

[0017] Through the above technical scheme, the present invention provides a compound used as an antioxidant in rubber, wherein the compound is cross-linked by a cross-linking agent, and the molecular weight becomes larger after cross-linking, which can enhance the migration resistance of the compound as an antioxidant. At the same time, by introducing epoxy groups through epoxy compounds, the compound has good dispersibility in rubber, and the compound has excellent comprehensive performance as an antioxidant; the compound has the protective performance of traditional antioxidants and the characteristic of migration resistance; the preparation method of the compound only requires simple separation and purification, and has the advantages of simple process and high product yield; in addition, the compound has good dispersibility in rubber, which can reduce the amount of rubber additives such as dispersants required for rubber refining. DETAILED DESCRIPTION

[0018] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0019] In a first aspect, the present invention provides a compound, wherein the compound comprises a cross-linked structure M and one or more structures A1 represented by formula (1) or structures A2 represented by formula (2) connected to the cross-linked structure M,

[0020]

[0021] Wherein, R1 is selected from H or R3 is selected from H or C1-C6 alkyl, R2 is selected from H or C1-C6 alkyl, R' is absent or R' is selected from C1-C 20 Oxygen-containing group, R" is selected from C1-C 20 Oxygen-containing groups;

[0022] The cross-linked structure M is selected from residues of tetraethyl orthosilicate, 3-glycidyloxypropyltrimethoxysilane or melamine.

[0023] In some embodiments of the present invention, R1 is selected from wherein R3 is selected from H or C1-C6 alkyl,

[0024] R' does not exist or is selected from R4 is absent or selected from wherein R5 is selected from C1-C6 alkylene ethers, wherein R6 is selected from C1-C 15 Alkyl ethers;

[0025] R" is selected from

[0026] In some specific embodiments of the present invention, R' does not exist, that is, R' may be absent in structure A1, that is, the cross-linking structure M is directly bonded to the N atom in structure A1.

[0027] In some specific embodiments of the present invention, R4 does not exist, which means that R4 may not exist, that is, the carbon atoms at both ends of R4 are directly bonded.

[0028] In some specific embodiments of the present invention, the molar ratio of the cross-linked structure M to the structure A1 or A2 is (1-3):(1-4).

[0029] In some specific embodiments of the present invention, the cross-linking structure M is selected from residues from tetraethyl orthosilicate, 3-glycidyloxypropyltrimethoxysilane (KH560) or melamine.

[0030] In some specific embodiments of the present invention, the cross-linked structure M can be selected from Among them, the cross-linked structure M can be bonded to the N atom in structure A1 (at this time, R' in structure A1 does not exist) through the C atom of the epoxy group in M, or the cross-linked structure M can be bonded to the O atom in R' in structure A1 through the Si atom in M, or the cross-linked structure M can be bonded to the O atom in R" in structure A2 through the Si atom in M, or the cross-linked structure M can be bonded to the C atom in R' in structure A1 through the N atom in M.

[0031] In the present invention, the sulfur-containing structure includes but is not limited to the above-mentioned structure.

[0032] In the present invention, since there is a cross-linked structure M in the compound and structure A1 or A2 is introduced at the same time, the obtained compound antioxidant has good thermal oxidative aging strength and excellent migration resistance. The compound is cross-linked by a cross-linking agent, and the molecular weight becomes larger after cross-linking, which can enhance the migration resistance of the compound as an antioxidant. At the same time, epoxy groups are introduced through epoxy compounds, and the compound has good dispersibility in rubber, and the compound has excellent comprehensive performance as an antioxidant.

[0033] In some specific embodiments of the present invention, the compound can be selected from at least one of the following compounds:

[0034]

[0035]

[0036] In the present invention, the compound structure includes but is not limited to the above structure.

[0037] In the present invention, the composition and structure of the compound can be determined by NMR, IR, GPC, elemental analysis, etc., or by preparing and feeding.

[0038] The second aspect of the present invention provides a method for preparing a compound, which comprises the following steps:

[0039] (1) subjecting an aniline compound to an addition reaction with an epoxy compound to obtain an intermediate product;

[0040] (2) in the presence of a catalyst, subjecting the intermediate product to a cross-linking reaction with a cross-linking agent to obtain the compound, wherein the cross-linking agent is a compound that does not contain an epoxy group;

[0041] Or include the following steps:

[0042] The compound is obtained by performing an addition cross-linking reaction between an aniline compound and a cross-linking agent, wherein the cross-linking agent is a compound containing an epoxy group.

[0043] In the present invention, if the crosslinking agent does not contain an epoxy group (such as tetraethyl orthosilicate), an epoxy compound (such as glycidyl methacrylate) needs to be added to the aniline compound to undergo an epoxy-amine addition reaction, and then the hydroxyl groups in the resulting product are crosslinked with the crosslinking agent. The reaction process is as follows:

[0044]

[0045] Among them, the hydroxyl group in the reaction product of the first step is not limited to reacting with the Si-O-C2H5 group at a specific position in the cross-linking agent, that is, it can react with the Si-O-C2H5 group at any position in the cross-linking agent.

[0046] If the cross-linking agent does not contain epoxy groups (such as melamine), an epoxy compound (such as diglycidyl ether) needs to be added to react with the aniline compound to undergo epoxy-amine addition reaction, and then the hydroxyl groups in the resulting product are cross-linked with the cross-linking agent. The reaction process is as follows:

[0047]

[0048] The epoxy group in the reaction product of the first step is not limited to reacting with the SH group at a specific position in the cross-linking agent, that is, it can react with the SH group at any position in the cross-linking agent.

[0049] If the crosslinking agent contains an epoxy group (such as KH560), the aniline compound and the crosslinking agent undergo an addition crosslinking reaction to produce an epoxy-amine addition reaction. The resulting product contains hydroxyl groups that are further crosslinked with the crosslinking agent. The reaction process is as follows:

[0050]

[0051] Among them, the R group of the product can contain an epoxy group and can continue to react with aniline compounds.

[0052] In some specific embodiments of the present invention, the aniline compound is selected from one or more of aniline, p-phenylenediamine, 4-aminodiphenylamine (RT base), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N,N'-di-sec-butyl-p-phenylenediamine (44PD) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD).

[0053] In some specific embodiments of the present invention, the epoxy compound is selected from one or more of methacrylate glycidyl ether, allyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, lauryl glycidyl ether and diglycidyl ether.

[0054] In the present invention, the aniline compound can be used to provide the structure A1 in the first aspect, or the aniline compound reacts with the epoxy compound to provide the structure A1 or structure A2 in the first aspect.

[0055] In some specific embodiments of the present invention, the crosslinking agent is selected from one or more of tetraethyl orthosilicate, 3-glycidyloxypropyltrimethoxysilane and melamine, to provide the crosslinking structure M in the first aspect.

[0056] In some specific embodiments of the present invention, the catalyst is selected from one or more of formic acid, salicylic acid and dibutyltin dilaurate.

[0057] In some specific embodiments of the present invention, the cross-linking reaction is carried out in a solvent, wherein the solvent is selected from one or more of benzene, xylene, 1,4-dioxane, dimethyl sulfoxide and n-heptane.

[0058] In some specific embodiments of the present invention, the addition reaction temperature is 110-150° C., and the addition reaction time is 3-10 h.

[0059] In some specific embodiments of the present invention, the cross-linking reaction temperature is 80-190° C., and the cross-linking reaction time is 3-15 h.

[0060] In some specific embodiments of the present invention, the addition cross-linking reaction temperature is 80-190° C., and the addition cross-linking reaction time is 3-15 h.

[0061] In some specific embodiments of the present invention, in step (1), the molar ratio of the aniline compound, the epoxy compound and the cross-linking agent is (0.1-0.5): (0.1-0.5): (0.01-0.5).

[0062] In some specific embodiments of the present invention, the molar ratio of the aniline compound to the cross-linking agent is (0.1-0.5): (0.01-0.5).

[0063] In the present invention, the composition and structure of the compound can be determined by NMR, IR, GPC, elemental analysis, etc., or by preparing and feeding.

[0064] The third aspect of the present invention provides a compound obtained by the preparation method.

[0065] The fourth aspect of the present invention provides a use of the compound as an antioxidant in rubber.

[0066] A fifth aspect of the present invention provides a rubber, wherein the rubber comprises raw rubber and the compound.

[0067] In some specific embodiments of the present invention, the compound is added to the rubber in an amount of 2-3 wt % of the raw rubber.

[0068] In some specific embodiments of the present invention, the mobility of the compound in the rubber is 1-5.5%.

[0069] The present invention will be described in detail below through examples.

[0070] In the following examples and comparative examples, if no specific conditions are specified, the reaction is carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained through commercial channels. The composition and structure of the compounds prepared in the following examples are determined by preparing the feed (after the reaction of the example is completed, the feed is basically reacted completely).

[0071] Example 1

[0072] 0.16 mol of RT base was dissolved in 1,4-dioxane and mixed with 0.05 mol of KH560, and reacted at 80° C. for 3 h under the catalysis of salicylic acid to obtain a reaction product mixture; the reaction product mixture was transferred to a rotary evaporator to remove the solvent and then cooled to room temperature to obtain compound P1;

[0073] The molar ratio of the cross-linked structure M to the structure A1 is 1:3; the cross-linked structure M comes from the residue of KH560, and the cross-linked structure M and the structure A1 are connected through the C atom of the epoxy group in KH560 and the N atom in the structure A1. The structure A1 is as shown in formula (1), wherein R' does not exist and R1 is R2 is H.

[0074] Example 2

[0075] Under nitrogen protection, 0.21 mol of RT base was dissolved in 1,4-dioxane and 0.2 mol of glycidyl methacrylate at 95°C for 1 hour, and the obtained product was mixed with 0.05 mol of tetraethyl orthosilicate, and reacted at 80°C for 3 hours under the catalysis of dibutyltin dilaurate to obtain a reaction product mixture; the reaction product mixture was transferred to a rotary evaporator to remove the solvent and then cooled to room temperature to obtain compound P2;

[0076] The molar ratio of the cross-linked structure M to the structure A1 is 1:4; the cross-linked structure M is derived from the residue of tetraethyl orthosilicate, and the cross-linked structure M and the structure A1 are connected via the Si atom in tetraethyl orthosilicate and the O atom in the structure A1, and the structure A1 is as shown in formula (1), wherein R' is R1 is R2 is H.

[0077] Example 3

[0078] 0.21 mol of IPPD was dissolved in 1,4-dioxane and reacted with 0.1 mol of diglycidyl ether at 105°C for 2 hours, and the obtained product was mixed with 0.05 mol of ethyl orthosilicate, and reacted at 80°C for 3 hours under the catalysis of dibutyltin dilaurate to obtain a reaction product mixture; the reaction product mixture was transferred to a rotary evaporator to remove the solvent and then cooled to room temperature to obtain compound P3;

[0079] The molar ratio of the cross-linked structure M to the structure A2 is 2:1; the cross-linked structure M is derived from the residue of tetraethyl orthosilicate, and the cross-linked structure M and the structure A2 are connected via the Si atom in tetraethyl orthosilicate and the O atom in the structure A2. The structure A2 is as shown in formula (2), wherein R" is R1 is R2 is isopropyl.

[0080] Example 4

[0081] 0.21 mol of IPPD was dissolved in 1,4-dioxane and reacted with 0.1 mol of diglycidyl ether at 105°C for 2 hours, and the obtained product was mixed with 0.05 mol of ethyl orthosilicate, and reacted at 80°C for 3 hours under the catalysis of dibutyltin dilaurate to obtain a reaction product mixed solution; the reaction product mixed solution was transferred to a rotary evaporator to remove the solvent and then cooled to room temperature to obtain compound P4;

[0082] The molar ratio of the cross-linked structure M to the structure A2 is 2:1; the cross-linked structure M is derived from the residue of tetraethyl orthosilicate, and the cross-linked structure M and the structure A2 are connected via the Si atom in tetraethyl orthosilicate and the O atom in the structure A2. The structure A2 is as shown in formula (2), wherein R" is R1 is R2 is isopropyl.

[0083] Example 5

[0084] 0.21 mol of 44PD was dissolved in 1,4-dioxane and reacted with 0.1 mol of diglycidyl ether at 105°C for 2 hours, and the obtained product was mixed with 0.05 mol of ethyl orthosilicate, and reacted at 80°C for 3 hours under the catalysis of dibutyltin dilaurate to obtain a reaction product mixed solution; the reaction product mixed solution was transferred to a rotary evaporator to remove the solvent and then cooled to room temperature to obtain compound P5;

[0085] The molar ratio of the cross-linked structure M to the structure A1 is 2:1; the cross-linked structure M is derived from the residue of tetraethyl orthosilicate, and the cross-linked structure M and the structure A2 are connected via the Si atom in tetraethyl orthosilicate and the O atom in the structure A2. The structure A2 is as shown in formula (2), wherein R" is R1 is R2 is isobutyl.

[0086] Example 6

[0087] Using DMSO as solvent, 0.15 mol of aniline and 0.15 mol of diglycidyl ether were reacted at 75°C for 5 hours, and the obtained product was mixed with 0.1 mol of melamine, and reacted at 180°C for 3 hours under the catalysis of salicylic acid to obtain a reaction product mixture; the reaction product mixture was transferred to a rotary evaporator to remove the solvent and then cooled to room temperature to obtain compound P6;

[0088] Among them, the cross-linked structure M comes from melamine, and the molar ratio of the cross-linked structure M to the structure A1 is 1:

[0089] 1.5; the cross-linked structure M is derived from the residue of melamine, and the cross-linked structure M and the structure A1 are connected through the N atom in melamine and the C atom in the structure A1, and the structure A1 is as shown in formula (1), wherein R' is R1 is H, and R2 is H.

[0090] Example 7

[0091] Using DMSO as solvent, 0.15 mol of p-phenylenediamine and 0.15 mol of diglycidyl ether were reacted at 75°C for 5 hours, and the obtained product was mixed with 0.05 mol of melamine, and reacted at 180°C for 3 hours under the catalysis of formic acid to obtain a reaction product mixed solution; the reaction product mixed solution was transferred to a rotary evaporator to remove the solvent and then cooled to room temperature to obtain compound P7;

[0092] The molar ratio of the cross-linked structure M to the structure A1 is 1:3; the cross-linked structure M is derived from the residue of melamine, and the cross-linked structure M and the structure A1 are connected via the N atom in melamine and the C atom in the structure A1. The structure A1 is as shown in formula (1), wherein R' is R1 is amino, and R2 is H.

[0093] Test Case

[0094] 100 parts by weight of natural rubber, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 45 parts by weight of carbon black N330, 1.5 parts by weight of accelerator, 2.5 parts by weight of insoluble sulfur and 2 parts by weight of compounds A1-A7 obtained in Examples 1-7 were mixed, kneaded and vulcanized to obtain vulcanized rubbers B1-B7. The standard dumbbell-shaped films were cut by a slicer and subjected to ozone aging test and migration resistance test respectively.

[0095] Comparative Test Example 1: 100 parts by weight of styrene-butadiene rubber, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 45 parts by weight of carbon black N660, 1.5 parts by weight of accelerator, 2.5 parts by weight of insoluble sulfur and 2 parts by weight of antioxidant IPPD were mixed, kneaded and vulcanized to obtain vulcanized rubber D1. Ozone aging test and migration resistance test were performed respectively.

[0096] Comparative Test Example 1: 100 parts by weight of styrene-butadiene rubber, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 45 parts by weight of carbon black N660, 1.5 parts by weight of accelerator, 2.5 parts by weight of insoluble sulfur and 2 parts by weight of antioxidant 6PPD were mixed, kneaded and vulcanized to obtain vulcanized rubber D2. Ozone aging test and migration resistance test were performed respectively.

[0097] In the ozone aging experiment, the aging temperature was set at 100°C and the ozone amount was 100ppm. The test sample was aged for 1 day, and the retention rate of the tensile strength of the material after 3 days was taken as the anti-aging efficiency. Retention rate = parameter after aging / parameter before aging × 100%.

[0098] The migration resistance test includes water extraction resistance and migration test. For water extraction resistance, two pieces of film weighing about 5g are completely immersed in 100ml deionized water. After soaking at room temperature for 14 days, the water is evaporated and made into 10ml methanol solution. The antioxidant content in the solution is detected by high performance liquid chromatography. For the migration test, the film is contacted with a blank film without antioxidant at a pressure of 1MPa and 90℃ for 300min. Acetone is used as a solvent to extract the blank film and test the antioxidant content in acetone. The results are shown in Table 1.

[0099] Table 1

[0100]

[0101] It can be seen from the results in Table 1 that the compound antioxidant obtained by Examples 1-7 of the present invention was used for performance testing. The tensile strength retention rate was high after ozone aging for 1 day and 3 days, and the water extraction rate and migration rate were only 1 / 10-1 / 5 of those in the comparative example. The antioxidant obtained by the technical solution of the present invention has good thermal oxygen aging strength and excellent migration resistance.

[0102] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A compound, characterized in that The compound contains a cross-linked structure M and one or more structures A1 represented by formula (1) or structures A2 represented by formula (2) connected to the cross-linked structure M. Wherein, R1 is selected from H or R3 is selected from H or C1-C6 alkyl, R2 is selected from H or C1-C6 alkyl, R' is absent or R' is selected from C1-C 20 Oxygen-containing group, R" is selected from C1-C 20 Oxygen-containing groups; The cross-linked structure M is selected from residues of tetraethyl orthosilicate, 3-glycidyloxypropyltrimethoxysilane or melamine.

2. The compound according to claim 1, characterized in that R1 is selected from wherein R3 is selected from H or C1-C6 alkyl, R' does not exist or is selected from R4 is absent or selected from wherein R5 is selected from C1-C6 alkylene ethers, wherein R6 is selected from C1-C 15 Alkyl ethers; R" is selected from 3. The compound according to claim 1 or 2, characterized in that The molar ratio of the cross-linked structure M to the structure A1 or A2 is (1-3):(1-4).

4. A method for preparing a compound, characterized in that: The steps include: (1) subjecting an aniline compound to an addition reaction with an epoxy compound to obtain an intermediate product; (2) in the presence of a catalyst, subjecting the intermediate product to a cross-linking reaction with a cross-linking agent to obtain the compound, wherein the cross-linking agent is a compound that does not contain an epoxy group; Or include the following steps: The compound is obtained by performing an addition cross-linking reaction between an aniline compound and a cross-linking agent, wherein the cross-linking agent is a compound containing an epoxy group.

5. The preparation method according to claim 4, characterized in that: The aniline compound is selected from one or more of aniline, p-phenylenediamine, 4-aminodiphenylamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine; Preferably, the crosslinking agent is selected from one or more of tetraethyl orthosilicate, 3-glycidyloxypropyltrimethoxysilane and melamine; Preferably, the epoxy compound is selected from one or more of methacrylate glycidyl ether, allyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, lauryl glycidyl ether and diglycidyl ether; Preferably, the catalyst is selected from one or more of formic acid, salicylic acid and dibutyltin dilaurate.

6. The preparation method according to claim 4 or 5, characterized in that: The addition reaction temperature is 110-150°C, and the addition reaction time is 3-10h; Preferably, the cross-linking reaction temperature is 80-190°C, and the cross-linking reaction time is 3-15h; Preferably, the addition cross-linking reaction temperature is 80-190° C., and the addition cross-linking reaction time is 3-15 h.

7. The preparation method according to any one of claims 4 to 6, characterized in that: When the cross-linking agent is a compound without epoxy group, the molar ratio of the aniline compound, the epoxy compound and the cross-linking agent is (0.1-0.5): (0.1-0.5): (0.01-0.5); Preferably, when the cross-linking agent is a compound containing an epoxy group, the molar ratio of the aniline compound to the cross-linking agent is (0.1-0.5): (0.01-0.5).

8. A compound obtained by the preparation method according to any one of claims 4 to 7.

9. Use of the compound according to any one of claims 1 to 3 and 8 as an antioxidant in rubber.

10. A rubber, characterized in that: The rubber comprises raw rubber and the compound according to any one of claims 1 to 3 and 8.

11. The rubber according to claim 10, characterized in that In the rubber, the compound is added in an amount of 2-3 wt% of the raw rubber; Preferably, the mobility of the compound in the rubber is 1-5.5%.

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