A phenolic anti-aging styrene-butadiene rubber and its preparation method

Abstract

This invention discloses a phenolic anti-aging styrene-butadiene rubber (SBR) and its preparation method, belonging to the field of rubber functionalization modification technology. The preparation method of the phenolic anti-aging SBR includes: firstly, epoxidizing the SBR with m-chloroperoxybenzoic acid; secondly, performing an epoxy ring-opening reaction with hydrochloric acid; and finally, esterifying with a phenolic antioxidant to obtain the phenolic anti-aging SBR. This invention grafts phenolic antioxidant functionalized side chains onto the SBR molecular chain through a three-step reaction of epoxy-ring-esterification, thereby improving the SBR's resistance to heat, oxygen, and ozone aging, while simultaneously solving the problem of small-molecule antioxidants easily migrating in the rubber matrix due to poor compatibility.

Description

Technical Field

[0001] This invention relates to the field of rubber functionalization modification technology, and more specifically, to a phenolic anti-aging styrene-butadiene rubber and its preparation method. Background Technology

[0002] Commonly used rubber materials, such as natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), and nitrile rubber (NBR), are diene rubbers. Due to the presence of numerous isolated unsaturated carbon-carbon double bonds and reactive allyl hydrogen structures in their main chains, they are prone to aging under conditions of oxygen, ozone, light, and heat. Thermo-oxidative aging and ozone aging, as the most common types of rubber aging, can significantly damage the physical or chemical properties of rubber materials, causing premature failure of rubber products. This not only wastes valuable rubber resources but can also seriously threaten human safety. Adding antioxidants to the rubber matrix is ​​the most convenient and effective way to inhibit the aging of rubber materials. However, these antioxidants, due to their low molecular weight, tend to migrate from the rubber matrix under low pressure, liquid, and high temperature conditions, thus reducing their protective effect. Furthermore, the migrated antioxidants can cause surface defects in rubber products and may even have toxic effects on the environment and human health.

[0003] Currently, amine antioxidants, especially p-phenylenediamine antioxidants, are widely used in various rubber products due to their good overall protective effect, wide variety, and low price. Although p-phenylenediamine antioxidants exhibit excellent resistance to heat, oxygen, and ozone aging, they suffer from low safety, high hazard, and high staining susceptibility, leading the EU to classify them as restricted compounds. Studies have shown that 6PPD-quinones, conversion products of p-phenylenediamine antioxidant 6PPD in tire wear particles, are chemicals contributing to urban coho salmon runoff mortality syndrome, which has adverse effects on both environmental protection and human health. Compared to amine antioxidants, phenolic antioxidants are more suitable for use in polymer materials due to their non-discoloration and non-polluting properties; however, their overall protective effect is not as good as that of amine antioxidants, limiting their application. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a phenolic anti-aging styrene-butadiene rubber and its preparation method. This invention grafts phenolic anti-aging functionalized side chains onto the styrene-butadiene rubber molecular chain through a three-step reaction of epoxy-ring-esterification, thereby improving the heat, oxygen, and ozone aging resistance of styrene-butadiene rubber. Simultaneously, it solves the problem of small-molecule antioxidants easily migrating in the rubber matrix due to poor compatibility.

[0005] One objective of this invention is to provide a phenolic anti-aging styrene-butadiene rubber, wherein the phenolic anti-aging styrene-butadiene rubber has the following structural formula:

[0006]

[0007] In the formula, a, b, c, d, e, and f correspond to the molar percentage of each repeating unit in the phenolic anti-aging styrene-butadiene rubber. Their values ​​depend on the molecular chain structure of the selected styrene-butadiene rubber. The preferred values ​​are: a: 15–35 mol%, b: 40–80 mol%, c: 5–35 mol%, d: 0.5–10 mol%, e: 0.5–10 mol%, and f: 0.5–10 mol%.

[0008] The phenolic side chain content (i.e., the molar percentage of repeating unit f) of the phenolic anti-aging styrene-butadiene rubber is 0.5-10 mol%, preferably 1-5 mol%.

[0009] The second objective of this invention is to provide a method for preparing phenolic anti-aging styrene-butadiene rubber, the method comprising:

[0010] First, styrene-butadiene rubber (SBR) is epoxidized with m-chloroperoxybenzoic acid, then subjected to an epoxy ring-opening reaction with hydrochloric acid, and finally esterified with a phenolic antioxidant to obtain the phenolic anti-aging SBR.

[0011] Preferably,

[0012] The method includes:

[0013] (1) Add m-chloroperoxybenzoic acid solution dropwise to styrene-butadiene rubber solution to carry out epoxidation reaction. After the reaction is completed, post-treatment is performed to obtain epoxidized styrene-butadiene rubber.

[0014] (2) Add hydrochloric acid solution dropwise to the solution of the epoxidized styrene-butadiene rubber dissolved in solvent A to carry out the epoxy ring-opening reaction. After the reaction is completed, post-treatment is performed to obtain hydroxylated styrene-butadiene rubber.

[0015] (3) Add phenolic antioxidant and acylation catalyst to the solution of the hydroxylated styrene-butadiene rubber dissolved in solvent B to carry out the activation reaction, and then add a two-electron affinity condensing agent to carry out the esterification reaction. After the reaction is completed, the phenolic anti-aging styrene-butadiene rubber is obtained by post-treatment.

[0016] Preferably,

[0017] In step (1):

[0018] The styrene-butadiene rubber mentioned is a commonly used styrene-butadiene rubber in the art, including but not limited to SBR1502;

[0019] The solvent for the m-chloroperoxybenzoic acid solution is tetrahydrofuran, a polar solvent capable of dissolving m-chloroperoxybenzoic acid and miscible with the solvent for dissolving styrene-butadiene rubber, forming a homogeneous reaction system; and / or,

[0020] The solvent of the styrene-butadiene rubber solution is at least one of cyclohexane, toluene, xylene, tetrahydrofuran, n-hexane, and dichloromethane.

[0021] Preferably,

[0022] In step (1):

[0023] The concentration of the m-chloroperoxybenzoic acid solution is 20wt% to 50wt%; and / or,

[0024] The concentration of the styrene-butadiene rubber solution is 5 wt% to 15 wt%; and / or,

[0025] The molar ratio of m-chloroperoxybenzoic acid to carbon-carbon double bonds in styrene-butadiene rubber is (0.10-0.20):1, preferably (0.12-0.15):1.

[0026] Preferably,

[0027] In step (1):

[0028] The epoxidation reaction is carried out at a temperature of 25℃ to 45℃ for a time of 1 to 4 hours; and / or,

[0029] The post-processing includes:

[0030] Alkali solution was added to the reaction solution to adjust the pH to 7-8. After flocculation in the flocculant, the epoxidized styrene-butadiene rubber was obtained by drying.

[0031] Preferably,

[0032] The alkaline solution is at least one of sodium hydroxide solution, sodium bicarbonate solution, and ammonia solution; and / or,

[0033] The flocculant is at least one of anhydrous ethanol and anhydrous methanol.

[0034] Preferably,

[0035] In step (2):

[0036] Solvent A is at least one selected from tetrahydrofuran, toluene, xylene, and dichloromethane; and / or,

[0037] The concentration of the hydrochloric acid solution is 20 wt% to 36.5 wt%; and / or,

[0038] The epoxidized styrene-butadiene rubber is dissolved in solvent A at a concentration of 5 wt% to 15 wt%; and / or,

[0039] The molar ratio of hydrochloric acid to the epoxy groups in the epoxidized styrene-butadiene rubber is (0.5-3):1, preferably (1-1.5):1.

[0040] Preferably,

[0041] In step (2):

[0042] The ring-opening reaction of the epoxy group is carried out at a temperature of 15℃ to 35℃ for a time of 2 to 4 hours; and / or,

[0043] The post-processing includes:

[0044] The reaction solution was flocculated in a flocculant and then dried to obtain the hydroxylated styrene-butadiene rubber.

[0045] Preferably,

[0046] The flocculant is at least one of anhydrous ethanol and anhydrous methanol.

[0047] Preferably,

[0048] In step (3):

[0049] Solvent B is at least one selected from dichloromethane, chloroform, diethyl ether, carbon tetrachloride, and toluene; and / or,

[0050] The hydroxylated styrene-butadiene rubber is dissolved in solvent B at a concentration of 5–15 wt%; and / or,

[0051] The phenolic antioxidant is a phenolic antioxidant containing a carboxyl group;

[0052] Preferably,

[0053] The carboxyl-containing phenolic antioxidant is at least one selected from 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, 3,5-di-tert-butylsalicylic acid, and 3,4,5-trihydroxybenzoic acid (gallic acid); and / or,

[0054] The molar ratio of the phenolic antioxidant to the hydroxyl groups in the hydroxylated styrene-butadiene rubber is (1-3):1, preferably (1.2-1.5):1; and / or,

[0055] The acylation catalyst is at least one selected from 4-dimethylaminopyridine (DMAP), 4-pyrrolidinylpyridine (4-PPY), 1-hydroxybenzotriazole, and N-hydroxy-7-azabenzotriazole. Through the acylation catalyst, the unstable intermediate generated during the activation reaction can be converted into the corresponding active ester or active amide, preventing it from forming a urea; and / or,

[0056] The molar ratio of the acylation catalyst to the hydroxyl groups in the hydroxylated styrene-butadiene rubber is (0.2–1):1, preferably (0.4–0.6):1; and / or,

[0057] The two-electron affinity condensing agent is a carbodiimide condensing agent;

[0058] Preferably,

[0059] The carbodiimide condensing agent is at least one of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), dicyclohexylcarbodiimide, and diisopropylcarbodiimide, which forms an amide or acyl ion intermediate with a carboxylic acid, the intermediate being capable of undergoing an acylation reaction; and / or,

[0060] The molar ratio of the two-electron affinity condensing agent to the hydroxyl group in the hydroxylated styrene-butadiene rubber is (1-3):1, preferably (1.5-1.8):1.

[0061] Preferably,

[0062] In step (3):

[0063] The activation reaction time is 1–4 hours, and the temperature is 20℃–35℃; and / or,

[0064] The esterification reaction time is 12–48 h, and the temperature is 20℃–35℃; and / or,

[0065] A protective gas is introduced during the esterification reaction;

[0066] Preferably,

[0067] The protective gas is at least one of nitrogen and inert gas;

[0068] More preferably,

[0069] The inert gas is argon, which can prevent the rubber and reagents from being oxidized during the reaction; and / or,

[0070] The post-processing includes:

[0071] After co-precipitation of the reaction solution in solvent C, washing and drying were performed to obtain the phenolic anti-aging styrene-butadiene rubber.

[0072] Preferably,

[0073] The solvent C is at least one of ethanol and methanol.

[0074] The following solutions can be adopted:

[0075] It includes three steps: epoxy oxidation, ring opening, and esterification.

[0076] (1) Add styrene-butadiene rubber to a three-necked flask containing solvent and stir at a certain speed until completely dissolved. The concentration of the rubber solution is 5wt% to 15wt%. Then, dissolve m-chloroperoxybenzoic acid (m-CPBA) in tetrahydrofuran. After it is completely dissolved, add it to a constant pressure dropping funnel for later use. The reaction temperature is 25℃ to 45℃. Open the constant pressure dropping funnel and slowly add the m-CPBA solution. The reaction is carried out for 1 to 4 hours. After the reaction is completed, add an alkaline solution to wash until the pH is 7 to 8. Then, flocculate the product in a flocculant and dissolve it in THF before flocculation. Repeat this process three times to remove the generated m-chlorobenzoic acid. Finally, dry the obtained product in a 60℃ forced-air drying oven to constant weight to obtain epoxidized styrene-butadiene rubber (e-ESBR).

[0077] (2) The product e-ESBR obtained in step (1) is added to a three-necked flask containing tetrahydrofuran and stirred at 200 r / min until completely dissolved, with a solution concentration of 5 wt% to 15 wt%. Then, a certain amount of HCl solution is added dropwise to the three-necked flask and reacted at 15℃ to 35℃ for 2 to 4 hours. After the reaction is completed, the product is flocculated in a flocculant and dissolved in THF before flocculation. This process is repeated three times to remove excess HCl. Finally, the obtained product is dried in a forced-air drying oven at 40℃ to constant weight to obtain hydroxylated styrene-butadiene rubber (HO-ESBR).

[0078] (3) Dissolve the product HO-ESBR obtained in step (2) in dried solvent B, then add phenolic antioxidant and acylation catalyst to the solution and stir to activate for 1-4 h, then add two-electron affinity condensing agent to the mixed solution, stir and introduce protective gas at room temperature, react for 24-48 h, then co-precipitate and wash the rubber solution in excess solvent C, and dry it in a forced-air oven at 55°C to obtain phenolic anti-aging styrene-butadiene rubber (ESBR-g-BHTA).

[0079] Because styrene-butadiene rubber (SBR) is prone to aging under conditions such as oxygen, ozone, light, and heat, antioxidants are often added to improve its aging resistance. Commonly used antioxidants for SBR are small-molecule p-phenylenediamine antioxidants, such as antioxidant 4010 and antioxidant 4020. These have poor compatibility with rubber and tend to migrate from the rubber matrix under low pressure, liquid, and high temperature conditions, thus reducing their protective effect. Furthermore, p-phenylenediamine antioxidants and their aging products are biotoxic, posing harmful effects to the environment and human health. Phenolic antioxidants have poor protective effects and often fail to achieve the required protective effect within a certain dosage range, limiting their application in rubber.

[0080] This invention improves the aging resistance of styrene-butadiene rubber (SBR) by introducing phenolic functionalized side chains onto the SBR molecular chain, while simultaneously addressing the problem of small-molecule antioxidants migrating out of the rubber matrix due to poor compatibility. Since phenolic antioxidants cannot directly react with SBR, this invention first introduces highly reactive epoxy groups into the rubber molecular chain through epoxidation with m-chloroperoxybenzoic acid. Then, hydrochloric acid is used to ring-open the epoxy groups, successfully introducing hydroxyl groups that can react with phenolic antioxidants onto the molecular chain. Finally, through the esterification reaction of the hydroxyl groups with carboxyl groups, a phenolic anti-aging SBR is successfully synthesized, exhibiting good resistance to heat, oxygen, and ozone aging. This solves the problems of easy aging of SBR during storage and use, easy migration of small-molecule antioxidants into the rubber matrix, and poor protective effect of phenolic antioxidants. Attached Figure Description

[0081] Figure 1 The 1H NMR spectra of commercially available styrene-butadiene rubber 1502, epoxidized styrene-butadiene rubber and hydroxylated styrene-butadiene rubber prepared in Example 1, and phenolic anti-aging styrene-butadiene rubber prepared in Examples 1, 7, 26, 27 and 29 are shown.

[0082] As shown in the figure, characteristic signal peaks representing the methylene protons of the trans and cis epoxy groups appeared at 2.98–2.92 ppm and 2.75–2.63 ppm, respectively, indicating the successful synthesis of epoxidized latex styrene-butadiene rubber. After ring-opening with HCl, the peaks of the epoxy groups in the epoxidized styrene-butadiene rubber completely disappeared. The peaks at 3.97 and 3.89 ppm correspond to the proton absorption peaks of the carbon atom attached to Cl, and the peaks at 3.72 and 3.61 ppm correspond to the proton absorption peaks of the carbon atom attached to OH. After ring-opening, because the polybutadiene unit in the epoxidized styrene-butadiene rubber has both cis and trans structures, there are two peaks, one high and one low, representing the OH structure. This is because the cis and trans structures have different polarities and coupling constants, resulting in different chemical shifts, indicating the successful synthesis of hydroxylated styrene-butadiene rubber. Phenolic antioxidants were grafted through activation and esterification reactions, resulting in peaks at 7.04 ppm and 5.12 ppm. The peak intensities of the 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid benzene ring, phenolic hydroxyl proton peak, methylene proton peak, and methyl proton peak appeared at ppm, 2.92ppm, 2.69ppm, and 1.47ppm, respectively. In addition, there were proton absorption peaks at 3.95ppm and 3.85ppm corresponding to the carbon atom connected to the chlorine atom, and at 3.72ppm and 3.62ppm corresponding to the remaining hydroxyl carbon. This proves that phenolic anti-aging styrene-butadiene rubber was successfully synthesized. With the increase of the amount of phenolic anti-aging functional side chain, the peak intensities of the 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid benzene ring, phenolic hydroxyl proton peak, methylene proton peak, and methyl proton peak increased at 7.04ppm, 5.12ppm, 2.92ppm, 2.69ppm, and 1.47ppm, respectively.

[0083] Figure 2 The static tensile test results of the phenolic anti-aging styrene-butadiene rubber prepared in Examples 1, 7 and 18, the commercially available styrene-butadiene rubber 1502 of Comparative Example 1, and the styrene-butadiene rubber with added commercial antioxidant BHT of Comparative Example 2 after 72 hours of ozone aging are shown in the figure.

[0084] The phenolic anti-aging styrene-butadiene rubbers prepared in Examples 1, 7 and 18, along with commercially available styrene-butadiene rubber 1502 from Comparative Example 1 and styrene-butadiene rubber with added commercial antioxidant BHT from Comparative Example 2, were subjected to ozone aging for 72 hours. The ozone cracking static tensile test was then performed using GB / T7762-1987.

[0085] from Figure 2 As can be seen, the phenolic anti-aging styrene-butadiene rubber prepared in Examples 1, 7 and 18 only showed fine cracks and did not break, while commercially available styrene-butadiene rubber 1502 (Comparative 1) and styrene-butadiene rubber with added commercial antioxidant BHT (Comparative Example 2) showed larger cracks and breakage, indicating that the phenolic anti-aging styrene-butadiene rubber of the present invention has better ozone aging resistance. Detailed Implementation

[0086] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0087] All raw materials used in the embodiments of this invention are commercially available products, and specific information is shown in Table 1:

[0088] Table 1

[0089]

[0090] Example 1

[0091] (1) 100g of styrene-butadiene rubber 1502 (with a butadiene content of 76.5%) was added to a three-necked flask containing cyclohexane and stirred at a certain speed until completely dissolved, resulting in a solution concentration of 10wt%. Then, 34.5g of m-chloroperoxybenzoic acid (m-CPBA) (purity 85%) (molar ratio of m-CPBA to carbon-carbon double bonds in styrene-butadiene rubber is 0.12:1) was dissolved in tetrahydrofuran to a concentration of 35wt%. After complete dissolution, the solution was added to a constant-pressure dropping funnel for later use. The styrene-butadiene rubber solution was heated to 35℃, and the m-CPBA solution was slowly added to the constant-pressure dropping funnel. The reaction was allowed to proceed for 1 hour. After the reaction was completed, 10% NaOH solution was added to wash the solution until the pH reached 7-8. The product was then flocculated in anhydrous ethanol and dissolved in THF before flocculation. This process was repeated three times to remove the generated m-chlorobenzoic acid. Finally, the obtained product was dried to constant weight in a forced-air drying oven at 60℃ to obtain epoxidized styrene-butadiene rubber e-ESBR with an epoxy degree of 10% (epoxy degree = (A 2.98-2.85 +A 2.77-2.64 ) / (A 5.50-5.10 +A 5.07-4.78 +A 2.77-2.64 +A 2.98-2.85 )×100%, the epoxy degree is based on the integral area A of the epoxy groups in the 1H NMR spectrum. 2.98-2.85 (inverse structure) and A 2.77-2.64 (cis structure); double bond integral area A 5.50-5.10 (1,4 bonus) and A 5.07-4.78 (Calculated using (1,2 addition)).

[0092] (2) 100g of the above-obtained product, epoxidized styrene-butadiene rubber e-ESBR (e-ESBR contains 109 mmol of epoxy groups), was added to a three-necked flask containing tetrahydrofuran and stirred at 200 r / min until completely dissolved, resulting in a solution concentration of 10 wt%. Then, 10.9g of 36.5% HCl solution (HCl to epoxy groups in epoxidized styrene-butadiene rubber in a molar ratio of 1:1) was added dropwise to the three-necked flask, and the reaction was carried out at 35℃ for 2 h. After the reaction was completed, the product was flocculated in anhydrous ethanol and dissolved in THF before flocculation. This process was repeated three times to remove excess HCl. Finally, the obtained product was dried in a forced-air drying oven at 40℃ to constant weight to obtain hydroxylated styrene-butadiene rubber HO-ESBR with a hydroxylation degree of 6% (hydroxylation degree = double bond content × epoxy degree × ring-opening rate, where ring-opening rate = A 3.70-3.50 / [A 3.70-3.50 +(A 2.98-2.85 +A 2.77-2.64 [) / 2]×100%, the ring-opening rate is based on the integral area A of the repeating hydroxyl structural unit in the 1H NMR spectrum. 3.70-3.50 The integral area A of the repeating unit of the epoxy group structure 2.98-2.85 and A2.77-2.64 Calculations show that the ring-opening rate is 80%, and the double bond content in styrene-butadiene rubber 1502 is 76.5 wt%.

[0093] (3) Dissolve 100g of the above-obtained product HO-ESBR (the hydroxyl group in HO-ESBR is 56mmol) in dried dichloromethane to a concentration of 10wt%. Then add 19.4g of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (BHTA) (the molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid to the hydroxyl group in hydroxylated styrene-butadiene rubber is 1.2:1) and 3.4g of 4-dimethylaminopyridine (DMAP) (the molar ratio of 4-dimethylaminopyridine to the hydroxyl group in hydroxylated styrene-butadiene rubber is 0.5:1). Stir and activate for 1h. Then add 16.5g of [unspecified ingredient] to the mixed solution. 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) (with a molar ratio of 1.5:1 of hydroxyl groups in 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride to hydroxylated styrene-butadiene rubber) was subjected to an esterification reaction, and nitrogen gas was introduced while stirring at room temperature. After reacting for 24 hours, the rubber solution was co-precipitated in excess ethanol, washed, and dried in a forced-air oven at 55°C to obtain phenolic anti-aging styrene-butadiene rubber (structural formula as follows).

[0094]

[0095] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.8 mol%, and 1.2 mol%, respectively, which means that the phenolic side chain content was 1.2 mol.

[0096] Example 2

[0097] The preparation method is basically the same as in Example 1, except that the solvent type and concentration of the styrene-butadiene rubber solution in the epoxidation reaction in step (1) are different. The solvent used is n-hexane and the concentration of the solution is 15 wt%.

[0098] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 58 mol%, 12 mol%, 1.4 mol%, 4.0 mol%, and 1.1 mol%, respectively, which means that the content of the phenolic side chain was 1.1 mol.

[0099] Example 3

[0100] The preparation method is basically the same as in Example 1, except that the solvent and the concentration of the styrene-butadiene rubber solution in the epoxidation reaction in step (1) are different. The solvent used is xylene and the concentration of the solution is 5 wt%.

[0101] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.8 mol%, and 1.2 mol%, respectively, which means that the phenolic side chain content was 1.2 mol.

[0102] Example 4

[0103] The preparation method is basically the same as that in Example 1, except that the reaction time and temperature of the epoxidation reaction in step (1) are different. The reaction time is 2 hours and the reaction temperature is 45°C.

[0104] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.8 mol%, and 1.2 mol%, respectively, which means that the phenolic side chain content was 1.2 mol.

[0105] Example 5

[0106] The preparation method is basically the same as that in Example 1, except that the reaction time and temperature of the epoxidation reaction in step (1) are different. The reaction time is 4 hours and the reaction temperature is 25°C.

[0107] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.8 mol%, and 1.2 mol%, respectively, which means that the phenolic side chain content was 1.2 mol.

[0108] Example 6

[0109] The preparation method is basically the same as in Example 1, except that the amount of m-chloroperoxybenzoic acid used in the epoxidation reaction in step (1) is 28.8g, that is, the molar ratio of m-chloroperoxybenzoic acid to carbon-carbon double bonds in styrene-butadiene rubber is 0.10:1.

[0110] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 59 mol%, 12 mol%, 1.0 mol%, 3.5 mol%, and 1.0 mol%, respectively, which means that the phenolic side chain content was 1.0 mol.

[0111] Example 7

[0112] The preparation method is basically the same as in Example 1, except that the amount of m-chloroperoxybenzoic acid used in the epoxidation reaction in step (1) is 57.5g, that is, the molar ratio of m-chloroperoxybenzoic acid to carbon-carbon double bonds in styrene-butadiene rubber is 0.20:1.

[0113] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 50 mol%, 12 mol%, 3.1 mol%, 9.2 mol%, and 2.2 mol%, respectively, which means that the phenolic side chain content was 2.2 mol.

[0114] Example 8

[0115] The preparation method is basically the same as in Example 1, except that the amount of hydrochloric acid used in the ring-opening reaction of the epoxy group in step (2) is 5.5g, and the molar ratio of hydrochloric acid to epoxy group is 0.5:1.

[0116] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 2.7 mol%, 3.8 mol%, and 1.0 mol%, respectively, which means that the phenolic side chain content was 1.0 mol.

[0117] Example 9

[0118] The preparation method is basically the same as in Example 1, except that the amount of hydrochloric acid used in the ring-opening reaction of the epoxy group in step (2) is 32.7g, that is, the molar ratio of hydrochloric acid to epoxy group is 3:1.

[0119] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 0.8 mol%, 4.9 mol%, and 1.8 mol%, respectively, which means that the phenolic side chain content was 1.8 mol.

[0120] Example 10

[0121] The preparation method is basically the same as in Example 1, except that the concentration of hydrochloric acid used in the ring-opening reaction of the epoxy group in step (2) is 20% and the amount is 19.9g, that is, the molar ratio of hydrochloric acid to epoxy group is 1:1.

[0122] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 2.7 mol%, 3.8 mol%, and 1.0 mol%, respectively, which means that the phenolic side chain content was 1.0 mol.

[0123] Example 11

[0124] The preparation method is basically the same as in Example 1, except that the concentration of hydrochloric acid used in the ring-opening reaction of the epoxy group in step (2) is 30% and the amount is 13.3g, that is, the molar ratio of hydrochloric acid to epoxy group is 1:1.

[0125] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 2.4 mol%, 4.0 mol%, and 1.1 mol%, respectively, which means that the phenolic side chain content was 1.1 mol.

[0126] Example 12

[0127] The preparation method is basically the same as in Example 1, except that the solvent A and the concentration of the adhesive solution used in the ring-opening reaction of the epoxy group in step (2) are different. Solvent A is toluene and the concentration of the adhesive solution is 5 wt%.

[0128] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 2.0 mol%, 4.5 mol%, and 1.0 mol%, respectively, which means that the phenolic side chain content was 1.0 mol.

[0129] Example 13

[0130] The preparation method is basically the same as in Example 1, except that the solvent A and the concentration of the adhesive solution used in the ring-opening reaction of the epoxy group in step (2) are different. Solvent A is dichloromethane and the concentration of the adhesive solution is 15 wt%.

[0131] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 2.2 mol%, 4.2 mol%, and 1.1 mol%, respectively, which means that the content of the phenolic side chain was 1.0 mol.

[0132] Example 14

[0133] The preparation method is basically the same as that in Example 1, except that the reaction time and temperature of the epoxy ring-opening reaction in step (2) are different. The reaction time is 3 hours and the reaction temperature is 35°C.

[0134] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.8 mol%, and 1.2 mol%, respectively, which means that the phenolic side chain content was 1.2 mol.

[0135] Example 15

[0136] The preparation method is basically the same as that in Example 1, except that the reaction time and temperature of the epoxy ring-opening reaction in step (2) are different. The reaction time is 4 hours and the reaction temperature is 15°C.

[0137] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.4 mol%, 4.8 mol%, and 1.3 mol%, respectively, which means that the content of the phenolic side chain was 1.3 mol.

[0138] Example 16

[0139] The preparation method is basically the same as in Example 1, except that the type of solvent B and the concentration of the adhesive solution used in the activation reaction in step (3) are different. Solvent B is chloroform and the concentration of the adhesive solution is 15 wt%.

[0140] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.8 mol%, and 1.2 mol%, respectively, which means that the phenolic side chain content was 1.2 mol.

[0141] Example 17

[0142] The preparation method is basically the same as in Example 1, except that the type of solvent B and the concentration of the adhesive solution used in the activation reaction in step (3) are different. Solvent B is toluene and the concentration of the adhesive solution is 5 wt%.

[0143] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.9 mol%, and 1.1 mol%, respectively, which means that the phenolic side chain content was 1.1 mol.

[0144] Example 18

[0145] The preparation method is basically the same as in Example 1, except that the amount of phenolic antioxidant 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (BHTA) used in step (3) for esterification reaction is 16.2g, that is, the molar ratio of phenolic antioxidant to hydroxyl groups in hydroxylated styrene-butadiene rubber is 1:1.

[0146] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 5.0 mol%, and 1.0 mol%, respectively, which means that the phenolic side chain content was 1.0 mol.

[0147] Example 19

[0148] The preparation method is basically the same as in Example 1. The only difference is that the amount of phenolic antioxidant 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid used in the esterification reaction in step (3) is 48.5g, that is, the molar ratio of phenolic antioxidant to hydroxyl groups in hydroxylated styrene-butadiene rubber is 3:1.

[0149] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.2 mol%, and 1.8 mol%, respectively, which means that the phenolic side chain content was 1.8 mol.

[0150] Example 20

[0151] The preparation method is basically the same as in Example 1. The only difference is that the acylation catalyst used in the activation reaction in step (3) is 4-pyrrolidinylpyridine, and the amount used is 4.3g, that is, the molar ratio of the acylation catalyst to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 0.5:1.

[0152] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 2.4 mol%, and 3.6 mol%, respectively, which means that the phenolic side chain content was 3.6 mol.

[0153] Example 21

[0154] The preparation method is basically the same as in Example 1. The only difference is that the acylation catalyst used in the activation reaction in step (3) is 1-hydroxybenzotriazole, and the amount used is 3.8g, that is, the molar ratio of the acylation catalyst to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 0.5:1.

[0155] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.7 mol%, and 1.3 mol%, respectively, which means that the content of the phenolic side chain was 1.3 mol.

[0156] Example 22

[0157] The preparation method is basically the same as that in Example 18, except that the amount of acylation catalyst 4-pyrrolidinylpyridine (4-PPY) used in the activation reaction in step (3) is 1.7g, that is, the molar ratio of 4-pyrrolidinylpyridine to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 0.2:1.

[0158] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.0 mol%, and 2.0 mol%, respectively, which means that the phenolic side chain content was 2.0 mol.

[0159] Example 23

[0160] The preparation method is basically the same as in Example 18, except that the amount of acylation catalyst 4-pyrrolidinylpyridine (4-PPY) used in the activation reaction in step (3) is 8.6g, that is, the molar ratio of 4-pyrrolidinylpyridine to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 1:1.

[0161] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 2.2 mol%, and 3.8 mol%, respectively, which means that the phenolic side chain content was 3.8 mol.

[0162] Example 24

[0163] The preparation method is basically the same as that in Example 18, except that the two-electron affinity condensing agent used in step (3) is dicyclohexylcarbodiimide, and the amount used is 17.6g, that is, the molar ratio of the two-electron affinity condensing agent to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 1.5:1.

[0164] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 4.5 mol%, and 1.5 mol%, respectively, which means that the phenolic side chain content was 1.5 mol.

[0165] Example 25

[0166] The preparation method is basically the same as that in Example 18, except that the two-electron affinity condensing agent used in step (3) is diisopropylcarbodiimide, and the amount used is 10.8g, that is, the molar ratio of the two-electron affinity condensing agent to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 1.5:1.

[0167] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 3.8 mol%, and 2.2 mol%, respectively, which means that the phenolic side chain content was 2.2 mol.

[0168] Example 26

[0169] The preparation method is basically the same as that in Example 18, except that the amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride used in the esterification reaction in step (3) is 11.1g, that is, the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 1:1.

[0170] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 3.2 mol%, and 2.8 mol%, respectively, which means that the phenolic side chain content was 2.8 mol.

[0171] Example 27

[0172] The preparation method is basically the same as that in Example 18, except that the amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride used in the esterification reaction in step (3) is 33.3g, that is, the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride to the hydroxyl group in the hydroxylated styrene-butadiene rubber is 3:1.

[0173] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 2.1 mol%, and 3.9 mol%, respectively, which means that the phenolic side chain content was 3.9 mol.

[0174] Example 28

[0175] The preparation method is basically the same as that in Example 18, except that the activation reaction time in step (3) is 4h, the activation reaction temperature is 20℃, the esterification reaction time is 48h, and the esterification reaction temperature is 20℃.

[0176] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 2.2 mol%, and 3.8 mol%, respectively, which means that the phenolic side chain content was 3.8 mol.

[0177] Example 29

[0178] The preparation method is basically the same as that in Example 18, except that the activation reaction time in step (3) is 2h, the activation reaction temperature is 35℃, the esterification reaction time is 12h, and the esterification reaction temperature is 35℃.

[0179] The percentages of the corresponding repeating units a, b, c, d, e, and f in the phenolic anti-aging styrene-butadiene rubber were calculated using the integral area of ​​the corresponding structures in the 1H NMR spectrum. These percentages were 23.5 mol%, 57 mol%, 12 mol%, 1.5 mol%, 2.7 mol%, and 3.3 mol%, respectively, which means that the content of the phenolic side chain was 3.3 mol.

[0180] Comparative Example 1

[0181] Commercial emulsion styrene-butadiene rubber 1502.

[0182] Comparative Example 2

[0183] Styrene-butadiene rubber with added commercial antioxidant BHT: Plasticize 100g of styrene-butadiene rubber 1502 on a two-roll mill, pass through the mill 1-2 times until it is evenly wrapped around the rolls, then widen the roll gap appropriately, add 3g of commercial antioxidant BHT and pass through the mill 3 times. After mixing evenly, form a triangular wrap 3 times and roll it 3 times. Adjust the roll gap to 2-3mm and then sheet it.

[0184] The properties of phenolic anti-aging styrene-butadiene rubber (SBR) prepared in the examples, commercial emulsion SBR 1502 (Comparative Example 1), and SBR with added commercial antioxidant BHT (Comparative Example 2) were compared: After testing the mechanical properties according to GB / T528-2009, the same batch of samples were aged in a thermo-oxidative aging oven at 100℃ for 72 hours. The mechanical properties after aging were tested according to GB / T528-2009, and the tensile aging coefficient was calculated. The tensile aging coefficient = (tensile strength after aging × elongation at break after aging) / (tensile strength before aging × elongation at break before aging) × 100%. The test results are shown in Table 2 below.

[0185] Table 2

[0186]

[0187] As shown in Table 2, the introduction of phenolic side chains into the rubber molecular chains of Examples 1-29 before thermo-oxidative aging further enhanced the polarity of the rubber, and the tensile strength of the rubber increased with the increase of phenolic side chain content. Simultaneously, the increased number of large side chains increased the spacing between molecular chains, acting as a plasticizer and increasing the elongation at break. After thermo-oxidative aging, the tensile strength of Examples 1-29 increased while the elongation at break decreased, while both the tensile strength and elongation at break of commercial styrene-butadiene rubber 1502 and the styrene-butadiene rubber with added commercial antioxidant BHT decreased. During thermo-oxidative aging, cross-linking is the main process for styrene-butadiene rubber, leading to hardening and brittleness and a decrease in elongation at break. Phenolic anti-aging styrene-butadiene rubber, due to the presence of chlorine atoms, undergoes ionic cross-linking between zinc oxide and chloride ions during aging at 100°C, resulting in increased tensile strength and decreased elongation at break. Commercial styrene-butadiene rubber 1502 and the styrene-butadiene rubber with added commercial antioxidant BHT lack such ionic cross-linking, and their tensile strength decreased after aging.

[0188] The tensile volume aging coefficient can characterize the change in rubber properties before and after aging. Compared with commercial styrene-butadiene rubber 1502 and styrene-butadiene rubber with added commercial antioxidant BHT, Examples 1-29 have a higher tensile volume aging coefficient, indicating that they have better resistance to heat and oxygen aging.

Claims

1. A phenolic age resistant styrene butadiene rubber characterized in that The phenolic anti-aging butadiene styrene rubber has a structural formula as follows: In the formula, a: 20-30 mol%; b: 30-45 mol%; c: 10-20 mol%; d: 1-5 mol%; e: 1-5 mol%; f: 1-5 mol%.

2. A method for preparing phenolic anti-aging styrene-butadiene rubber as described in claim 1, characterized in that... The method comprises: First, the butadiene styrene rubber is subjected to an epoxidation reaction by means of meta-chloroperoxybenzoic acid, then subjected to an epoxy group ring-opening reaction with hydrochloric acid, and finally subjected to an esterification reaction with a phenolic antioxidant to obtain the phenolic anti-aging butadiene styrene rubber.

3. The preparation method of phenolic anti-aging styrene-butadiene rubber according to claim 2, characterized in that... The method comprises: (1) The meta-chloroperoxybenzoic acid solution is added dropwise into a butadiene styrene rubber solution to perform an epoxidation reaction, after the reaction is completed, post-treatment is performed to obtain an epoxidized butadiene styrene rubber; (2) The hydrochloric acid solution is added dropwise into a solution of the epoxidized butadiene styrene rubber dissolved in a solvent A to perform an epoxy group ring-opening reaction, after the reaction is completed, post-treatment is performed to obtain a hydroxylated butadiene styrene rubber; (3) The phenolic antioxidant and an acylation catalyst are added into a solution of the hydroxylated butadiene styrene rubber dissolved in a solvent B to perform an activation reaction, then a double-electronophile condensing agent is added to perform an esterification reaction, after the reaction is completed, post-treatment is performed to obtain the phenolic anti-aging butadiene styrene rubber.

4. The preparation method of the phenolic anti-aging butadiene styrene rubber according to claim 3, characterized in that: In step (1), the solvent of the meta-chloroperoxybenzoic acid solution is tetrahydrofuran; and / or, The solvent of the butadiene styrene rubber solution is at least one of cyclohexane, toluene, xylene, tetrahydrofuran, n-hexane and dichloromethane.

5. The preparation method of the phenolic anti-aging butadiene styrene rubber according to claim 3, characterized in that: In step (1), the concentration of the meta-chloroperoxybenzoic acid solution is 20wt%-50wt%; and / or, The concentration of the butadiene styrene rubber solution is 5wt%-15wt%; and / or, The molar ratio of the meta-chloroperoxybenzoic acid to the carbon-carbon double bond in the butadiene styrene rubber is (0.10-0.20):

1.

6. The preparation method of the phenolic anti-aging butadiene styrene rubber according to claim 5, characterized in that: The molar ratio of the meta-chloroperoxybenzoic acid to the carbon-carbon double bond in the butadiene styrene rubber is (0.12-0.15):

1.

7. The preparation method of the phenolic anti-aging butadiene styrene rubber according to claim 3, characterized in that: In step (1), the temperature of the epoxidation reaction is 25°C-45°C, and the time is 1-4h; and / or, The post-treatment comprises: The pH value of the reaction liquid is adjusted to 7-8 by adding an alkali solution, and after flocculation in a flocculating agent, the epoxidized butadiene styrene rubber is obtained by drying.

8. The preparation method of the phenolic anti-aging butadiene styrene rubber according to claim 7, characterized in that: The alkali solution is at least one of a sodium hydroxide solution, a sodium bicarbonate solution and ammonia water; and / or, The flocculating agent is at least one of anhydrous ethanol and anhydrous methanol.

9. The preparation method of the phenolic anti-aging butadiene styrene rubber according to claim 3, characterized in that: In step (2), the solvent A is at least one of tetrahydrofuran, toluene, xylene and dichloromethane; and / or, The concentration of the hydrochloric acid solution is 20wt%-36.5wt%; and / or, ​ ​ ​ ​ The solution concentration of the epoxidized styrene-butadiene rubber dissolved in the solvent A is 5wt%-15wt%; and / or, The molar ratio of the hydrochloric acid to the epoxy group in the epoxidized styrene-butadiene rubber is (0.5-3):

1.

10. The preparation method of the phenolic anti-aging styrene-butadiene rubber according to claim 9, characterized in that: The molar ratio of the hydrochloric acid to the epoxy group in the epoxidized styrene-butadiene rubber is (1-1.5):

1.

11. The preparation method of the phenolic anti-aging styrene-butadiene rubber according to claim 3, characterized in that: In step (2): The temperature of the epoxy group ring-opening reaction is 15°C-35°C, and the time is 2-4h; and / or, The post-treatment comprises: After the reaction solution is flocculated in the flocculating agent, the hydroxylated styrene-butadiene rubber is obtained by drying.

12. The preparation method of the phenolic anti-aging styrene-butadiene rubber according to claim 11, characterized in that: The flocculating agent is at least one of anhydrous ethanol and anhydrous methanol.

13. The preparation method of the phenolic anti-aging styrene-butadiene rubber according to claim 3, characterized in that: In step (3): The solvent B is at least one of dichloromethane, chloroform, diethyl ether, carbon tetrachloride and toluene; and / or, The solution concentration of the hydroxylated styrene-butadiene rubber dissolved in the solvent B is 5wt%-15wt%; and / or, The phenolic anti-aging agent is a phenolic anti-aging agent containing a carboxyl group.

14. The preparation method of the phenolic anti-aging styrene-butadiene rubber according to claim 13, characterized in that: The phenolic anti-aging agent containing a carboxyl group is at least one of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, 3,5-di-tert-butylsalicylic acid and 3,4,5-trihydroxybenzoic acid; and / or, The molar ratio of the phenolic anti-aging agent to the hydroxyl group in the hydroxylated styrene-butadiene rubber is (1-3):1; and / or, The acylation catalyst is at least one of 4-dimethylaminopyridine, 4-pyrrolidinylpyridine, 1-hydroxybenzotriazole and N-hydroxy-7-azabenzotriazole; and / or, The molar ratio of the acylation catalyst to the hydroxyl group in the hydroxylated styrene-butadiene rubber is (0.2-1):1; and / or, The di-electrophile condensing agent is a carbodiimide condensing agent.

15. The preparation method of the phenolic anti-aging styrene-butadiene rubber according to claim 14, characterized in that: The molar ratio of the phenolic anti-aging agent to the hydroxyl group in the hydroxylated styrene-butadiene rubber is (1.2-1.5):1; and / or, The molar ratio of the acylation catalyst to the hydroxyl group in the hydroxylated styrene-butadiene rubber is (0.4-0.6):1; and / or, The carbodiimide condensing agent is at least one of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, dicyclohexylcarbodiimide and diisopropylcarbodiimide; and / or, The molar ratio of the di-electrophile condensing agent to the hydroxyl group in the hydroxylated styrene-butadiene rubber is (1-3):

1.

16. The preparation method of the phenolic anti-aging styrene-butadiene rubber according to claim 15, characterized in that: The molar ratio of the double electron affinity condensing agent to the hydroxyl group in the hydroxylated styrene-butadiene rubber is (1.5-1.8):

1. 17.The method according to claim 3, wherein the phenolic anti-aging styrene-butadiene rubber is prepared by the following steps: (1) preparing a double electron affinity condensing agent; (2) preparing a hydroxylated styrene-butadiene rubber; (3) condensing the double electron affinity condensing agent and the hydroxylated styrene-butadiene rubber to obtain a phenolic anti-aging styrene-butadiene rubber. In step (3), the activation reaction time is 1-4 h, and the temperature is 20-35℃; and / or, the esterification reaction time is 12-48 h, and the temperature is 20-35℃; and / or, a protective gas is introduced during the esterification reaction; and / or, the post-treatment comprises: After the reaction solution is co-precipitated in solvent C, the phenolic anti-aging styrene-butadiene rubber is obtained by washing and drying. 18.The method according to claim 17, wherein the phenolic anti-aging styrene-butadiene rubber is prepared by the following steps: (1) preparing a double electron affinity condensing agent; (2) preparing a hydroxylated styrene-butadiene rubber; (3) condensing the double electron affinity condensing agent and the hydroxylated styrene-butadiene rubber to obtain a phenolic anti-aging styrene-butadiene rubber. In step (3), the protective gas is at least one of nitrogen and an inert gas; and / or, the solvent C is at least one of ethanol and methanol. 19.The method according to claim 18, wherein the phenolic anti-aging styrene-butadiene rubber is prepared by the following steps: (1) preparing a double electron affinity condensing agent; (2) preparing a hydroxylated styrene-butadiene rubber; (3) condensing the double electron affinity condensing agent and the hydroxylated styrene-butadiene rubber to obtain a phenolic anti-aging styrene-butadiene rubber. In step (3), the inert gas is argon. ​

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