Copolymer, preparation method and application thereof, and rubber

Abstract

The invention relates to the field of rubber anti-aging agents, and discloses a copolymer, a preparation method and application thereof, and rubber. Wherein the copolymer comprises a structural unit A as shown in a formula (1), a structural unit B as shown in a formula (2), a formula (3) or a formula (4), # imgabs 0 # imgabs 1 #, R1 is selected from H, C1-C6 alkyl, amino or # imgabs 2 #, R5 is selected from H or C1-C6 alkyl, R2 is selected from H or C1-C6 alkyl, and R3 is selected from H or C1-C6 alkyl; r1 is selected from H or C1-C4 alkyl, R2 is selected from H or C1-C4 alkyl, R3 is selected from H or C1-C4 alkyl, R4 is selected from H or C1-C6 alkyl, and R6 is selected from H or C1-C4 alkyl. The copolymer serving as a rubber anti-aging agent has medium and long-term protection performance of a traditional anti-aging agent and also has the characteristic of migration resistance; the preparation method of the rubber anti-aging agent has the advantages of simple process, high product yield and the like; in addition, the molecular weight of the rubber anti-aging agent can be autonomously regulated and controlled, and the rubber anti-aging agent has better dispersity in rubber.

Description

Technical Field

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

[0002] 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 largely caused a sharp decline in the number of salmon populations.

[0003] CN113620988A discloses a formula of a composite rubber antioxidant, which is a reactive antioxidant synthesized from p-phenylenediamine as a basic raw material. This type of antioxidant contains both active groups that can react with rubber macromolecules and groups that have the function of inhibiting rubber aging, and has the characteristics of non-migration, non-volatility and non-extraction.

[0004] CN112980217A proposes a method for modifying a graphene oxide (GO)-silicon dioxide (SiO2) composite filler to solve the problem of poor dispersion and easy agglomeration of GO and SiO2 in rubber. At the same time, the composite filler is endowed with anti-aging properties by modifying GO. However, a large amount of the composite filler added will affect the vulcanization performance of the rubber.

[0005] CN108203414A discloses a method for preparing a macromolecular antioxidant TMPPD, which has antioxidant and anti-aging properties and certain migration resistance characteristics, and can avoid environmental problems caused by the migration of the antioxidant to a certain extent. However, the process for preparing the antioxidant is complicated and the reaction conversion rate is low. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems of the prior art that the rubber antioxidant has poor protective performance, is easy to migrate, has poor dispersibility in rubber, has a complex process flow and has a low reaction conversion rate, and to provide a copolymer and a preparation method and application thereof and a rubber.

[0007] In order to achieve the above object, the present invention provides a copolymer in a first aspect, wherein the copolymer comprises: a structural unit A represented by formula (1), a structural unit B represented by formula (2), formula (3) or formula (4),

[0008]

[0009] Wherein, R1 is selected from H, C1-C6 alkyl, amino or Wherein R5 is selected from H or C1-C6 alkyl; R2 is selected from H or C1-C4 alkyl, R3 is selected from H or C1-C4 alkyl, R4 is selected from H or C1-C6 alkyl, and R6 is selected from H or C1-C4 alkyl.

[0010] The second aspect of the present invention provides a method for preparing a copolymer, which comprises the following steps:

[0011] (1) in the presence of an initiator, subjecting a compound a represented by formula (5), an alkenyl epoxy compound b, and a molecular regulator to a first reaction to obtain a first product;

[0012] (2) subjecting the compound c represented by formula (6) to a second reaction with the first product to obtain the copolymer;

[0013]

[0014] Among them, the definitions of R1, R2, R3, and R4 are the same as those described in the first aspect.

[0015] The third aspect of the present invention provides a copolymer obtained by the preparation method.

[0016] The fourth aspect of the present invention provides a use of the copolymer as an antioxidant in rubber.

[0017] A fifth aspect of the present invention provides a rubber, wherein the rubber comprises raw rubber and the copolymer.

[0018] Through the above technical scheme, the present invention provides a copolymer used as an antioxidant in rubber, wherein the copolymer antioxidant obtained by introducing structural unit A and structural unit B into the copolymer has good thermal oxidative aging strength, excellent migration resistance, and better compatibility between the antioxidant with aromatic group and the rubber with aromatic group. As a rubber antioxidant, the copolymer has the medium- and long-term protective performance of traditional antioxidants, and also has the characteristics of migration resistance; the preparation method of the rubber antioxidant has the advantages of simple process and high product yield; in addition, the molecular weight of the rubber antioxidant can be independently regulated, and it has good dispersibility in rubber. DETAILED DESCRIPTION

[0019] 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.

[0020] The first aspect of the present invention provides a copolymer, wherein the copolymer comprises: a structural unit A represented by formula (1), a structural unit B represented by formula (2), formula (3) or formula (4),

[0021]

[0022] Wherein, R1 is selected from H, C1-C6 alkyl, amino or Wherein R5 is selected from H or C1-C6 alkyl; R2 is selected from H or C1-C4 alkyl, R3 is selected from H or C1-C4 alkyl, R4 is selected from H or C1-C6 alkyl, and R6 is selected from H or C1-C4 alkyl.

[0023] In the present invention, the copolymer antioxidant obtained by introducing the structural unit A and the structural unit B into the copolymer has good heat-oxidative aging strength, excellent migration resistance, and better compatibility between the antioxidant with aromatic group and the aromatic rubber. The above structural units are respectively bonded to form the copolymer through addition polymerization of the carbon-carbon double bonds contained in the corresponding monomers.

[0024] In some specific embodiments of the present invention, the molar ratio of the structural unit A to the structural unit B is (1-2): (2-4).

[0025] In some specific embodiments of the present invention, the molecular weight of the copolymer is 25000-60000 g / mol.

[0026] In some specific embodiments of the present invention, the copolymer may be selected from at least one of the following copolymers:

[0027] Copolymer-1, containing structural unit A is The structural unit B contained is Among them, the structural unit A contained in The molar ratio of the structural unit A to the structural unit B is 11:1;

[0028] Copolymer-2, containing structural unit A is The structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1;

[0029] Copolymer-3, containing structural unit A is The structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1;

[0030] Copolymer-4, containing structural unit A is The structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1;

[0031] Copolymer-5, containing structural unit A is The structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1;

[0032] Copolymer-6, containing structural unit A is The structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1.

[0033] The second aspect of the present invention provides a method for preparing a copolymer, which comprises the following steps:

[0034] (1) in the presence of an initiator, subjecting a compound a represented by formula (3), an alkenyl epoxy compound b, and a molecular regulator to a first reaction to obtain a first product;

[0035] (2) subjecting the compound c represented by formula (4) to a second reaction with the first product to obtain the copolymer;

[0036]

[0037] Among them, the definitions of R1, R2, R3, and R4 are the same as those described in the first aspect.

[0038] In some specific embodiments of the present invention, the compound a is selected from one or more of styrene, divinylbenzene and α-methylstyrene.

[0039] In some specific embodiments of the present invention, the alkenyl epoxy compound b is selected from one or more of vinyl ethylene oxide, glycidyl methacrylate or propyl glycidyl ether.

[0040] In some specific embodiments of the present invention, the compound c 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), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD).

[0041] In some specific embodiments of the present invention, the initiator is selected from one or more of dibenzoyl peroxide, diisopropylbenzene peroxide and azobisisobutyronitrile, and is used to initiate the addition polymerization of the carbon-carbon double bonds contained in the compound a and the alkenyl epoxy compound b to obtain the first product.

[0042] In some specific embodiments of the present invention, the molecular regulator is selected from one or more of tert-dodecyl mercaptan, α-methylstyrene dimer and 2,6-di-tert-butyl-p-cresol. The molecular regulator can be used to adjust the polymerization degree of each of the structural unit A and the structural unit B in the obtained copolymer.

[0043] In some specific embodiments of the present invention, the first reaction and the second reaction need to be carried out under solvent conditions, wherein the solvent is selected from benzene and / or xylene.

[0044] In some specific embodiments of the present invention, the first reaction temperature is 50-85° C., and the first reaction time is 2-5 h.

[0045] In some specific embodiments of the present invention, the second reaction temperature is 110-150° C., and the second reaction time is 3-10 h.

[0046] In some specific embodiments of the present invention, in step (1), the molar ratio of compound a to alkenyl epoxy compound b is (0.01-1): (0.001-0.1); relative to 1 mol of compound a, the molecular regulator is 5-15 g, and the initiator is 1-5 g; in step (2), relative to 1-10 g of the first product, the compound c is 0.001-0.1 mol.

[0047] In the present invention, the composition and structure of the copolymer can be determined by NMR, IR, GPC, elemental analysis, etc., or by preparing and feeding.

[0048] The third aspect of the present invention provides a copolymer obtained by the preparation method.

[0049] The fourth aspect of the present invention provides a use of the copolymer as an antioxidant in rubber.

[0050] A fifth aspect of the present invention provides a rubber, wherein the rubber comprises raw rubber and the copolymer.

[0051] In some specific embodiments of the present invention, the copolymer is added in an amount of 2-3 wt % of the raw rubber in the rubber, preferably an aromatic-containing rubber, such as styrene-butadiene rubber.

[0052] In some specific embodiments of the present invention, the mobility of the copolymer in the rubber is 1-2.5%.

[0053] The present invention will be described in detail below through examples.

[0054] In the following examples and comparative examples, if no specific conditions are specified, the experiments are carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are conventional products that can be obtained through commercial channels. The composition and structure of the compounds described in the following examples and comparative examples can be determined by nuclear magnetic resonance, infrared, GPC, elemental analysis, etc., or by preparing and feeding.

[0055] Example 1

[0056] 0.1 mol of styrene, 0.01 mol of divinylbenzene, 0.01 mol of vinyl ethylene oxide, 1.0 g of tert-dodecyl mercaptan and 50 mL of xylene were sequentially added to a four-necked round-bottom flask, stirred to fully dissolve, and then nitrogen was introduced for replacement for 5 minutes, the temperature was raised to 85°C for stabilization, and then 50 mL of 0.5 wt% dibenzoyl peroxide / xylene solution was gradually added dropwise through a constant pressure dropping funnel. During the reaction for 2 hours, a white precipitate gradually appeared, which was washed with methanol, filtered and dried to obtain an intermediate product; 0.01 mol of 4-aminodiphenylamine (RT base), 5 g of the intermediate product and 50 mL of xylene were sequentially added to a single-necked round-bottom flask, the temperature was raised to 150°C for stabilization, and the reaction was continued for 5 hours, and after the reaction mixture was cooled to room temperature, methanol was added and stirred to precipitate the precipitate, which was washed, filtered and dried to obtain copolymer A1;

[0057] The weight average molecular weight of copolymer A1 is 35000 g / mol, and the structural unit A contained is The structural unit B contained is Among them, the structural unit A contained in The molar ratio of structural unit A to structural unit B is 0.1:0.01; the molar ratio of structural unit A to structural unit B is 11:1.

[0058] Example 2

[0059] 0.1 mol of styrene, 0.01 mol of vinyl ethylene oxide and 50 mL of xylene were sequentially added to a four-necked round-bottom flask, stirred to fully dissolve, and then nitrogen was introduced for replacement for 5 minutes, the temperature was raised to 85°C for stabilization, and then 50 mL of 0.5 wt% dibenzoyl peroxide / xylene solution was gradually added dropwise using a constant pressure dropping funnel. During the reaction for 2 hours, a white precipitate gradually appeared, which was washed with methanol, filtered, and dried to obtain an intermediate product; 0.01 mol of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), 5 g of the intermediate product and 50 mL of xylene were sequentially added to a single-necked round-bottom flask, the temperature was raised to 150°C for stabilization, and the reaction was continued for 5 hours after the reaction mixture was cooled to room temperature, methanol was added, stirred to precipitate the precipitate, and the copolymer A2 was obtained after washing, filtering, and drying;

[0060] The weight average molecular weight of copolymer A2 is 30000 g / mol, and the structural unit A contained is , the structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1.

[0061] Example 3

[0062] 0.1 mol of styrene, 0.01 mol of glycidyl methacrylate, 1.0 g of tert-dodecyl mercaptan and 50 mL of xylene were sequentially added to a four-necked round-bottom flask, stirred to fully dissolve, and then nitrogen was introduced for replacement for 5 minutes, the temperature was raised to 85°C for stabilization, and then 50 mL of 0.5 wt% dibenzoyl peroxide / xylene solution was gradually added dropwise with a constant pressure dropping funnel. During the reaction for 2 hours, a white precipitate gradually appeared, which was washed with methanol, filtered, and dried to obtain an intermediate product; 0.01 mol of N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 5 g of the intermediate product and 50 mL of xylene were sequentially added to a single-necked round-bottom flask, the temperature was raised to 150°C for stabilization, and the reaction was continued for 5 hours after the reaction mixture was cooled to room temperature, methanol was added, stirred to precipitate the precipitate, and the copolymer A3 was obtained after washing, filtering, and drying;

[0063] The weight average molecular weight of copolymer A3 is 45000 g / mol, and the structural unit A contained is , the structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1.

[0064] Example 4

[0065] 0.1 mol of styrene, 0.01 mol of allyl glycidyl ether, 1.0 g of tert-dodecyl mercaptan and 50 mL of xylene were sequentially added to a four-necked round-bottom flask, stirred to fully dissolve, and then nitrogen was introduced for replacement for 5 min, the temperature was raised to 85° C. for stabilization, and then 50 mL of 0.5 wt % dibenzoyl peroxide / xylene solution was gradually added dropwise with a constant pressure dropping funnel. During the reaction for 2 h, a white precipitate gradually appeared, which was washed with methanol, filtered and dried to obtain an intermediate product; 0.01 mol of N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 5 g of the intermediate product and 50 ml of xylene were sequentially added to a single-necked round-bottom flask, and the temperature was raised to 150° C. for stabilization after sufficient dissolution, and then reacted for 5 h. After the reaction mixture was cooled to room temperature, methanol was added and stirred to precipitate the precipitate, which was washed, filtered and dried to obtain copolymer A4; the possible reaction equation is as follows:

[0066]

[0067] The weight average molecular weight of copolymer A4 is 50000 g / mol, and the structural unit A contained is , the structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1.

[0068] Example 5

[0069] 0.1 mol of styrene, 0.01 mol of allyl glycidyl ether, 1.0 g of tert-dodecyl mercaptan and 50 mL of xylene were sequentially added to a four-necked round-bottom flask, stirred to fully dissolve, and then nitrogen was introduced for replacement for 5 minutes, the temperature was raised to 85°C for stabilization, and then 50 mL of 0.5 wt% dibenzoyl peroxide / xylene solution was gradually added dropwise with a constant pressure dropping funnel. During the reaction for 2 hours, a white precipitate gradually appeared, which was washed with methanol, filtered, and dried to obtain an intermediate product; 0.01 mol of N,N'-di-sec-butyl-p-phenylenediamine (44PD), 5 g of the intermediate product and 50 mL of xylene were sequentially added to a single-necked round-bottom flask, the temperature was raised to 150°C for stabilization, and the reaction was continued for 5 hours after the reaction mixture was cooled to room temperature, methanol was added, stirred to precipitate the precipitate, and the copolymer A5 was obtained after washing, filtering, and drying;

[0070] The weight average molecular weight of copolymer A5 is 40000 g / mol, and the structural unit A contained is , the structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1.

[0071] Example 6

[0072] 0.1 mol of styrene, 0.01 mol of allyl glycidyl ether, 1.0 g of tert-dodecyl mercaptan and 50 mL of xylene were sequentially added to a four-necked round-bottom flask, stirred to fully dissolve, and then nitrogen was introduced for replacement for 5 minutes, the temperature was raised to 85°C for stabilization, and then 50 mL of 0.5 wt% dibenzoyl peroxide / xylene solution was gradually added dropwise with a constant pressure dropping funnel. During the reaction for 2 hours, a white precipitate gradually appeared, which was washed with methanol, filtered, and dried to obtain an intermediate product; 0.01 mol of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), 5 g of the intermediate product and 50 mL of xylene were sequentially added to a single-necked round-bottom flask, the temperature was raised to 150°C for stabilization, and the reaction was continued for 5 hours after the reaction mixture was cooled to room temperature, methanol was added, stirred to precipitate the precipitate, and the copolymer A6 was obtained after washing, filtering, and drying;

[0073] The weight average molecular weight of copolymer A6 is 30000 g / mol, and the structural unit A contained is , the structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1.

[0074] Example 7

[0075] 0.1 mol of styrene, 0.01 mol of allyl glycidyl ether, 1.0 g of tert-dodecyl mercaptan and 50 mL of xylene were sequentially added to a four-necked round-bottom flask, stirred to fully dissolve, and then nitrogen was introduced for replacement for 5 minutes, the temperature was raised to 85°C for stabilization, and then 50 mL of 0.5 wt% dibenzoyl peroxide / xylene solution was gradually added dropwise with a constant pressure dropping funnel. During the reaction for 2 hours, a white precipitate gradually appeared, which was washed with methanol, filtered and dried to obtain an intermediate product; 0.01 mol of 7PPD, 5 g of the intermediate product and 50 mL of xylene were sequentially added to a single-necked round-bottom flask, the temperature was raised to 110°C for stabilization after sufficient dissolution, and the reaction was continued for 10 hours. After the reaction mixture was cooled to room temperature, methanol was added and stirred to precipitate the precipitate, which was washed, filtered and dried to obtain copolymer A7;

[0076] The weight average molecular weight of copolymer A7 is 55000 g / mol, and the structural unit A contained is , the structural unit B contained is Wherein, the molar ratio of structural unit A to structural unit B is 10:1.

[0077] Test Case

[0078] 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 N330, 1.5 parts by weight of accelerator, 2.5 parts by weight of insoluble sulfur and 2 parts by weight of copolymers 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 thermal oxidation aging test and migration resistance test respectively.

[0079] Test comparative 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 and kneaded, and vulcanized to obtain vulcanized rubber D1, and thermal oxidation aging test and migration resistance test were respectively carried out.

[0080] Test comparative example 2: 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 and kneaded, and vulcanized to obtain vulcanized rubber D2, and thermal oxidation aging test and migration resistance test were respectively carried out.

[0081] In the thermal oxygen aging experiment, the aging temperature was set at 100°C, and the test sample was aged for 3 days. The retention rate of the tensile strength of the material after 7 days was taken as the anti-aging efficiency, and the retention rate (%) = parameter after aging / parameter before aging × 100%.

[0082] The migration resistance test includes water extraction resistance and migration test. For water extraction resistance, two pieces of film weighing about 5g were completely immersed in 100mL deionized water. After soaking at room temperature for 14 days, the water was evaporated and made into 10mL methanol solution. The antioxidant content in the solution was detected by high performance liquid chromatography. For the migration test, the film was contacted with a blank film without antioxidant at a pressure of 1MPa and 90℃ for 300min. Acetone was used as a solvent to extract the blank film and test the antioxidant content in acetone. The results are shown in Table 1.

[0083] Table 1

[0084]

[0085] It can be seen from the results in Table 1 that the copolymer antioxidant obtained by Examples 1-7 of the present invention was used for performance testing. The tensile strength retention rate after 3 days and 7 days of thermal oxidative aging was high, and the water extraction rate and migration rate were only 1 / 10 of those in the comparative example. The antioxidant obtained by the technical solution of the present invention has good thermal oxidative aging strength and excellent migration resistance.

[0086] 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 copolymer, characterized in that The copolymer comprises: a structural unit A represented by formula (1), a structural unit B represented by formula (2), formula (3) or formula (4), Wherein, R1 is selected from H, C1-C6 alkyl, amino or Wherein R5 is selected from H or C1-C6 alkyl; R2 is selected from H or C1-C4 alkyl, R3 is selected from H or C1-C4 alkyl, R4 is selected from H or C1-C6 alkyl, and R6 is selected from H or C1-C4 alkyl.

2. The copolymer according to claim 1, characterized in that The molar ratio of the structural unit A to the structural unit B is (1-2): (2-4).

3. The copolymer according to claim 1 or 2, characterized in that in, The weight average molecular weight of the copolymer is 25000-60000 g / mol.

4. The copolymer according to any one of claims 1 to 3, characterized in that The copolymer is selected from at least one of the following copolymers: Copolymer-1, containing structural unit A is The structural unit B contained is Copolymer-2, containing structural unit A is The structural unit B contained is Copolymer-3, containing structural unit A is The structural unit B contained is Copolymer-4, containing structural unit A is The structural unit B contained is Copolymer-5, containing structural unit A is The structural unit B contained is Copolymer-6, containing structural unit A is The structural unit B contained is 5. A method for preparing a copolymer, characterized in that: The steps include: (1) in the presence of an initiator, subjecting a compound a represented by formula (5), an alkenyl epoxy compound b, and a molecular regulator to a first reaction to obtain a first product; (2) subjecting the compound c represented by formula (6) to a second reaction with the first product to obtain the copolymer; The definitions of R1, R2, R3, and R4 are the same as those in any one of claims 1 to 4.

6. The preparation method according to claim 5, characterized in that: The compound a is selected from one or more of styrene, divinylbenzene and α-methylstyrene; Preferably, the alkenyl epoxy compound b is selected from one or more of vinyl ethylene oxide, glycidyl methacrylate and allyl glycidyl ether; Preferably, the compound c 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, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine; Preferably, the initiator is selected from one or more of dibenzoyl peroxide, diisopropylbenzene peroxide and azobisisobutyronitrile; Preferably, the molecular regulator is selected from one or more of tert-dodecyl mercaptan, α-methylstyrene dimer and 2,6-di-tert-butyl-p-cresol.

7. The preparation method according to any one of claims 5 to 6, characterized in that: The first reaction temperature is 50-85°C, and the first reaction time is 2-5h; Preferably, the second reaction temperature is 110-150° C., and the second reaction time is 3-10 h.

8. The preparation method according to any one of claims 5 to 7, characterized in that: In step (1), the molar ratio of compound a to alkenyl epoxy compound b is (0.01-1): (0.001-0.1); Preferably, relative to 1 mol of compound a, the molecular regulator is 5-15 g, and the initiator is 1-5 g; Preferably, in step (2), the amount of compound c is 0.001-0.1 mol relative to 1-10 g of the first product.

9. The copolymer obtained by the preparation method according to any one of claims 5 to 8.

10. Use of the copolymer according to any one of claims 1 to 4 and 9 as an antioxidant in rubber.

11. A rubber, characterized in that: The rubber comprises raw rubber and the copolymer according to any one of claims 1 to 4 and 9; Preferably, in the rubber, the copolymer is added in an amount of 2-3 wt% of the raw rubber; Preferably, the mobility of the copolymer in the rubber is 1-2.5%.

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