A rubber based on N,N'-di-sec-butyl-p-phenylenediamine and its preparation method

Abstract

The present invention discloses a rubber based on N,N'-di-sec-butyl-p-phenylenediamine and a preparation method thereof. In the present invention, nano-zinc oxide is used as a reinforcing agent for the rubber, so that the rubber has good corrosion resistance, tear resistance, elasticity and elongation rate. By grafting organic substances for modification, the interfacial compatibility between nano-zinc oxide and the rubber is improved, the aggregation and agglomeration of nano-zinc oxide are reduced, and the tear resistance and elasticity of the rubber are improved. Long-chain alkanes can be inserted into the rubber polymer molecular chains, enhancing the movement ability of the rubber molecular chain segments, and improving the cold resistance of the rubber material. Nano-zinc oxide and quaternary ammonium salts can produce a synergistic antibacterial effect to avoid rubber mildew. The modified molecules can also be used in combination with a phosphorus-based flame retardant to achieve a synergistic flame retardant effect, endowing the rubber with flame retardant properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of rubber, and specifically relates to a rubber based on N,N'-di-sec-butyl-p-phenylenediamine and a preparation method thereof. Background Art

[0002] Rubber has high elasticity, can produce large deformations under very small external forces, and can return to its original state after the external force is removed. It can be artificially synthesized and has a low price. It has a wide range of applications and exists in all aspects of our lives. The molecular chains of rubber can be crosslinked. When the crosslinked rubber is deformed under the action of an external force, it has the ability to quickly recover, and has good physical and mechanical properties and chemical stability. Rubber is the basic raw material of the rubber industry and is widely used in the manufacture of tires, rubber hoses, tapes, cables and other various rubber products. However, common rubber is prone to oxidation, is liable to produce cracks at low temperatures, becomes hard and brittle, lacks elasticity, and can burn and continue to burn under specific conditions. It can be optimized by adding a series of additives such as antioxidants and reinforcing agents. Common antioxidants include N,N'-di-sec-butyl-p-phenylenediamine, which can be used as a general antioxidant for natural rubber and synthetic rubber. A reinforcing agent is a compounding agent that can improve the wear resistance, tear resistance or tensile strength of vulcanized rubber. Commonly used rubber reinforcing fillers are fine particle carbon black, white carbon black, zinc oxide, etc., but they are liable to aggregate and agglomerate in rubber, affecting their dispersibility, and their compatibility with rubber can be improved by modifying them. Summary of the Invention

[0003] The purpose of the present invention is to overcome the defects of the prior art and provide a rubber based on N,N'-di-sec-butyl-p-phenylenediamine and a preparation method thereof.

[0004] The purpose of the present invention can be achieved by the following technical solutions:

[0005] A rubber based on N,N'-di-sec-butyl-p-phenylenediamine is processed from the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 1-5 parts of hydroxy silicone oil, 1-2 parts of N,N'-di-sec-butyl-p-phenylenediamine, 1-2 parts of hydrogen-containing polysiloxane, 0.2-0.8 part of N-tert-butyl-2-benzothiazole sulfenamide, 0.5-1 part of tricresyl phosphate, and 1-3 parts of modified nano zinc oxide.

[0006] Further, the used modified nano zinc oxide is prepared by the following steps:

[0007] S1. Put cyanuric chloride and ethanol into a three-necked flask, control the temperature at 0 - 5 °C, stir for 5 min. Dissolve 1-nonylamine and triethylamine in ethanol, and slowly drip them into the three-necked flask using a constant-pressure dropping funnel. After the dropping is completed, continue the reaction for 3 h. After the reaction is completed, rotary evaporate under reduced pressure to remove ethanol. Wash the solid successively with 0.5 mol / L dilute hydrochloric acid and saturated brine, and then place it in a vacuum drying oven at 50 °C for 6 h to obtain Intermediate 1. The dosage ratio of cyanuric chloride, 1-nonylamine, and triethylamine is 10 g:7.75 g:5.5 g;

[0008] Under the action of the acid-binding agent triethylamine, the -Cl on the cyanuric chloride molecule reacts with the -NH on the 1-nonylamine molecule 2 to undergo a nucleophilic substitution reaction. By controlling the molar ratio of the two to be 1:1, the following reaction process occurs to obtain Intermediate 1;

[0009]

[0010] S2. Put Intermediate 1 and pyridine into a three-necked flask, then add ethanol as a solvent, control the heating temperature at 80 °C, and reflux for 5 h. After the reaction is completed, rotary evaporate under reduced pressure to remove the solvent to obtain Intermediate 2. The dosage ratio of Intermediate 1, pyridine, and ethanol is 10 g:2.7 g:100 mL;

[0011] Control the molar ratio of Intermediate 1 and pyridine to be 1:1. The tertiary nitrogen on the pyridine molecule undergoes an alkylation reaction with Intermediate 1 to obtain a quaternary ammonium product. The specific reaction process is as follows:

[0012]

[0013] S3. Put Intermediate 2 and tetrahydrofuran into a three-necked flask, stir at room temperature for 10 min. Dissolve glycine methyl ester and sodium carbonate in tetrahydrofuran, and slowly drip them into the three-necked flask using a constant-pressure dropping funnel. After the dropping is completed, react at room temperature for 4 h. After the reaction is completed, rotary evaporate to remove tetrahydrofuran. Wash the solid with saturated NaCl aqueous solution multiple times, and place it in a vacuum drying oven at 50 °C for 8 h to obtain Intermediate 3. The dosage ratio of Intermediate 2, glycine methyl ester, and sodium carbonate is 10 g:2.6 g:3.2 g;

[0014] Under the action of sodium carbonate, the -Cl on the Intermediate 2 molecule reacts with the -NH on the glycine methyl ester molecule 2 to undergo a nucleophilic substitution reaction. By controlling the molar ratio of the two to be close to 1:1, the following chemical reaction occurs to obtain Intermediate 3:

[0015]

[0016] S4. Add intermediate 3 into a flask equipped with a thermometer and a constant pressure dropping funnel, then add ethanol as the solvent, stir for 10 min, dropwise add saturated sodium hydroxide aqueous solution, after the addition is completed, react for 2 h. After the reaction is completed, dropwise add 4 mol / L hydrochloric acid until the pH = 2.5, react for 30 min, rotary evaporate the reaction solution under reduced pressure, wash the obtained solid with NaCl aqueous solution and deionized water successively until neutral to obtain intermediate 4; the dosage ratio of intermediate 3, ethanol and saturated sodium hydroxide aqueous solution is 10 g: 100 mL: 50 mL;

[0017] The ester group on the molecule of intermediate 3 is hydrolyzed to form a carboxyl group to obtain intermediate 4. The specific reaction process is as follows:

[0018]

[0019] S5. Add intermediate 4 and triethylamine into a flask, add DMF as the solvent, then add amino-functionalized nano-zinc oxide and DIC (N,N-diisopropylcarbodiimide), introduce nitrogen for protection, then ultrasonicate for 15 min, and then react at room temperature for 5 h. After the reaction is completed, centrifuge the reaction solution, wash it with DMF and ethanol aqueous solution 2 - 3 times successively, and finally dry the product in a vacuum oven at 50 °C for 6 h to obtain modified nano-zinc oxide; the dosage ratio of intermediate 4, triethylamine, amino-functionalized nano-zinc oxide and DIC is 10 g: 2.8 g: 2.6 g: 3.5 g;

[0020] Under the action of triethylamine and DIC, -NH grafted on the surface of amino-functionalized nano-zinc oxide 2 undergoes an amidation reaction with -COOH on the molecule of intermediate 4 to obtain modified nano-zinc oxide.

[0021] Nano-zinc oxide is used as a reinforcing agent for rubber, which can endow rubber with good corrosion resistance, tear resistance, elasticity and elongation at break. However, due to its large specific surface area and interfacial effect, the high-active particle surface of nano-zinc oxide is extremely prone to aggregation and agglomeration, which affects its dispersibility. By grafting organic substances for modification, the interfacial compatibility between nano-zinc oxide and rubber can be improved, the aggregation and agglomeration of nano-zinc oxide can be reduced, and the tear resistance and elasticity of rubber can be improved. Long-chain alkanes can be inserted into the rubber polymer molecular chain, weakening the stress between polymer chains, increasing the mobility of polymer molecular chains, reducing the crystallinity of polymer molecular chains, playing a "lubricating" role for rubber molecular segments, enhancing the movement ability of rubber molecular segments, and improving the cold resistance of rubber materials.

[0022] Under ultraviolet irradiation, the water or hydroxyl groups adsorbed on the surface of nano-zinc oxide are transformed into hydroxyl radicals, and the adsorbed oxygen is transformed into active oxygen. Hydroxyl radicals and active oxygen have extremely strong chemical activities and can kill most bacteria and viruses. The quaternary ammonium salt structure has a long-lasting bactericidal effect and can effectively enhance the persistence of the bactericidal effect. The two can produce a synergistic antibacterial effect to prevent rubber mildew.

[0023] During the combustion process, the triazine and imino groups on the modified molecule generate non-combustible gases such as nitrogen and nitrogen oxides, which act as foaming agents and coke strengtheners. The phosphorus-based flame retardant acts as a dehydrating agent and a carbon-forming agent. The two are used in combination to achieve a synergistic flame retardant effect, making the rubber have flame retardant properties.

[0024] Further, the amino-functionalized nano-zinc oxide is prepared by the following steps:

[0025] First, dissolve the silane coupling agent KH550 in an ethanol aqueous solution with a volume fraction of 40%, stir at room temperature for 30 min, add nano-zinc oxide, control the heating temperature at 80 °C, reflux for 1.5 h, centrifuge, wash 3 times with the ethanol aqueous solution, dry, and grind to obtain amino-functionalized nano-zinc oxide; the dosage ratio of the silane coupling agent KH550, ethanol aqueous solution, and nano-zinc oxide is 30 g: 300 mL: 10 g.

[0026] Another object of the present invention is to provide a preparation method of a rubber based on N,N'-di-sec-butyl-p-phenylenediamine, including the following steps:

[0027] First step, knead methyl vinyl silicone rubber, hydroxyl silicone oil, and modified nano-zinc oxide evenly in a kneader, heat-treat at 120 °C for 30 min, cool to room temperature, add N,N'-di-sec-butyl-p-phenylenediamine, hydrogen-containing polysiloxane, N-tert-butyl-2-benzothiazole sulfenamide, and tricresyl phosphate, and mix and stir evenly with a planetary mixer;

[0028] Second step, vulcanize and mold the kneaded mixture by molding at 140 °C to obtain a rubber based on N,N'-di-sec-butyl-p-phenylenediamine.

[0029] The beneficial effects of the present invention:

[0030] The present invention uses nano-zinc oxide as a reinforcing agent for rubber, so that the rubber has good corrosion resistance, tear resistance, elasticity and elongation. By grafting organic substances for modification, the interfacial compatibility between nano-zinc oxide and rubber is improved, the aggregation and agglomeration of nano-zinc oxide are reduced, the tear resistance and elasticity of the rubber are improved. The long-chain alkane can be inserted into the rubber polymer molecular chain, enhancing the movement ability of the rubber molecular chain segments, and improving the cold resistance of the rubber material. Nano-zinc oxide and quaternary ammonium salt can produce a synergistic antibacterial effect to avoid rubber mildew. The triazine and imino groups on the modified molecule generate incombustible gases such as nitrogen and nitrogen oxides during the combustion process, acting as a foaming agent and a coke reinforcing agent. The phosphorus-based flame retardant acts as a dehydrating agent and a carbonizing agent. The two are used in combination to achieve a synergistic flame retardant effect, making the rubber have flame retardant properties. Detailed implementation mode

[0031] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0032] Example 1

[0033] Preparation of amino-functionalized nano-zinc oxide:

[0034] First, dissolve 30 g of silane coupling agent KH550 in 300 mL of an ethanol aqueous solution with a volume fraction of 40%. Stir at room temperature for 30 min, add 10 g of nano-zinc oxide, control the heating temperature at 80 °C, reflux for 1.5 h, centrifuge, wash with ethanol aqueous solution three times, dry, and grind to obtain amino-functionalized nano-zinc oxide.

[0035] Example 2

[0036] Preparation of modified nano-zinc oxide:

[0037] S1. Put 10 g of cyanuric chloride and ethanol into a three-necked flask, control the temperature at 0 - 5 °C, stir for 5 min, dissolve 7.75 g of 1-nonamine and 5.5 g of triethylamine in ethanol, and slowly drip them into the three-necked flask with a constant pressure dropping funnel. After the dropping is completed, continue to react for 3 h. After the reaction is completed, remove ethanol by rotary evaporation under reduced pressure. Wash the solid with 0.5 mol / L dilute hydrochloric acid and saturated brine in sequence, and then place it in a vacuum drying oven at 50 °C for 6 h to obtain intermediate 1;

[0038] S2. Put 10 g of intermediate 1 and 2.7 g of pyridine into a three-necked flask, add 100 mL of ethanol as a solvent, control the heating temperature at 80 °C, reflux for 5 h. After the reaction is completed, remove the solvent by rotary evaporation under reduced pressure to obtain intermediate 2;

[0039] S3. Add 10 g of Intermediate 2 and tetrahydrofuran into a three-necked flask, stir at room temperature for 10 min. Dissolve 2.6 g of glycine methyl ester and 3.2 g of sodium carbonate in tetrahydrofuran, and slowly drip them into the three-necked flask using a constant-pressure dropping funnel. After the dropping is completed, react at room temperature for 4 h. After the reaction is completed, rotary evaporate to remove tetrahydrofuran. Wash the solid with saturated NaCl aqueous solution for several times, and place it in a vacuum drying oven at 50 °C for drying for 8 h to obtain Intermediate 3;

[0040] S4. Add 10 g of Intermediate 3 into a flask equipped with a thermometer and a constant-pressure dropping funnel, then add 100 mL of ethanol as a solvent, stir for 10 min, drip 50 mL of saturated sodium hydroxide aqueous solution. After the dropping is completed, react for 2 h. After the reaction is completed, drip 4 mol / L hydrochloric acid until the pH = 2.5, react for 30 min, rotary evaporate the reaction solution under reduced pressure. Wash the obtained solid with NaCl aqueous solution and deionized water successively until neutral to obtain Intermediate 4;

[0041] S5. Add 10 g of Intermediate 4 and 2.8 g of triethylamine into a flask, add DMF as a solvent, then add 2.6 g of the amino-functionalized nano-zinc oxide prepared in Example 1 and 3.5 g of DIC (N,N-diisopropylcarbodiimide), introduce nitrogen for protection, then ultrasonicate for 15 min, and then react at room temperature for 5 h. After the reaction is completed, centrifuge the reaction solution, wash it with DMF and ethanol aqueous solution for 2 - 3 times successively. Finally, place the product in a vacuum oven at 50 °C for drying for 6 h to obtain the modified nano-zinc oxide.

[0042] Example 3

[0043] Preparation of modified nano-zinc oxide:

[0044] S1. Put 20 g of cyanuric chloride and ethanol into a three-necked flask, control the temperature at 0 - 5 °C, stir for 5 min. Dissolve 15.5 g of 1-nonamine and 11 g of triethylamine in ethanol, and slowly drip them into the three-necked flask using a constant-pressure dropping funnel. After the dropping is completed, continue to react for 3 h. After the reaction is completed, rotary evaporate under reduced pressure to remove ethanol. Wash the solid with 0.5 mol / L dilute hydrochloric acid and saturated brine successively, and then place it in a vacuum drying oven at 50 °C for drying for 6 h to obtain Intermediate 1;

[0045] S2. Add 20 g of Intermediate 1 and 5.4 g of pyridine into a three-necked flask, then add 200 mL of ethanol as a solvent, control the heating temperature at 80 °C, and reflux for 5 h. After the reaction is completed, rotary evaporate under reduced pressure to remove the solvent to obtain Intermediate 2;

[0046] S3. Add 20 g of intermediate 2 and tetrahydrofuran into a three-necked flask, stir at room temperature for 10 min. Dissolve 5.2 g of glycine methyl ester and 6.4 g of sodium carbonate in tetrahydrofuran, and slowly drip them into the three-necked flask with a constant pressure dropping funnel. After the dropping is completed, react at room temperature for 4 h. After the reaction is completed, rotary evaporate to remove tetrahydrofuran. Wash the solid with saturated NaCl aqueous solution for several times, and place it in a vacuum drying oven at 50 °C for drying for 8 h to obtain intermediate 3;

[0047] S4. Add 20 g of intermediate 3 into a flask equipped with a thermometer and a constant pressure dropping funnel, then add 200 mL of ethanol as a solvent, stir for 10 min, drip 100 mL of saturated sodium hydroxide aqueous solution. After the dripping is completed, react for 2 h. After the reaction is completed, drip 4 mol / L hydrochloric acid until pH = 2.5, react for 30 min, and rotary evaporate the reaction solution under reduced pressure. Wash the obtained solid with NaCl aqueous solution and deionized water in turn until neutral to obtain intermediate 4;

[0048] S5. Add 20 g of intermediate 4 and 5.6 g of triethylamine into a flask, add DMF as a solvent, then add 5.2 g of the amino-functionalized nano-zinc oxide prepared in Example 1 and 7 g of DIC (N,N-diisopropylcarbodiimide), introduce nitrogen protection, then ultrasonicate for 15 min, and then react at room temperature for 5 h. After the reaction is completed, centrifuge the reaction solution, wash it with DMF and ethanol aqueous solution for 2 - 3 times in turn, and finally place the product in a vacuum oven at 50 °C for drying for 6 h to obtain modified nano-zinc oxide.

[0049] Example 4

[0050] First step, knead 100 g of methyl vinyl silicone rubber, 1 g of hydroxyl silicone oil, and 1 g of the modified nano-zinc oxide prepared in Example 2 evenly in a kneader, heat-treat at 120 °C for 30 min. After cooling to room temperature, add 1 g of N,N'-di-sec-butyl-p-phenylenediamine, 1 g of hydrogen-containing polysiloxane, 0.2 g of N-tert-butyl-2-benzothiazole sulfenamide, and 0.5 g of tricresyl phosphate, and mix and stir evenly using a planetary stirrer;

[0051] Second step, vulcanize and mold the kneaded mixture by molding at 140 °C to obtain a rubber based on N,N'-di-sec-butyl-p-phenylenediamine.

[0052] Example 5

[0053] First step: Knead 100 g of methyl vinyl silicone rubber, 3 g of hydroxy silicone oil, and 2 g of the modified nano-zinc oxide prepared in Example 3 evenly in a kneader, heat-treat at 120 °C for 30 min, after cooling to room temperature, add 1.5 g of N,N'-di-sec-butyl-p-phenylenediamine, 1.5 g of hydrogen-containing polysiloxane, 0.5 g of N-tert-butyl-2-benzothiazole sulfenamide, and 0.75 g of tricresyl phosphate, and mix and stir evenly using a planetary mixer;

[0054] Second step: Vulcanize and mold the kneaded mixture by molding at 140 °C to obtain a rubber based on N,N'-di-sec-butyl-p-phenylenediamine.

[0055] Example 6

[0056] First step: Knead 100 g of methyl vinyl silicone rubber, 5 g of hydroxy silicone oil, and 3 g of the modified nano-zinc oxide prepared in Example 2 evenly in a kneader, heat-treat at 120 °C for 30 min, after cooling to room temperature, add 2 g of N,N'-di-sec-butyl-p-phenylenediamine, 2 g of hydrogen-containing polysiloxane, 0.8 g of N-tert-butyl-2-benzothiazole sulfenamide, and 1 g of tricresyl phosphate, and mix and stir evenly using a planetary mixer;

[0057] Second step: Vulcanize and mold the kneaded mixture by molding at 140 °C to obtain a rubber based on N,N'-di-sec-butyl-p-phenylenediamine.

[0058] Control Example 1

[0059] Compared with Example 4, during the preparation process, ordinary nano-zinc oxide was used to replace the modified nano-zinc oxide, and the other raw materials and the preparation process remained unchanged, obtaining a rubber based on N,N'-di-sec-butyl-p-phenylenediamine.

[0060] For the rubbers based on N,N'-di-sec-butyl-p-phenylenediamine obtained in Examples 4 - 6 and Control Example 1, the following performance tests were carried out: Test the low-temperature elasticity according to the standard GB / T5564-94; Test the tear resistance according to the standard GB532-1989; Test the high-temperature resistance according to the standard GB / T3512-1983; Test the flame retardancy according to the standard UL-94; Test the anti-mildew performance according to the standard HG / T4301-2012, test strains: Aspergillus niger CGMCC3.5487, Penicillium funiculosum CGMCC3.3875, Chaetomium globosum CGMCC3.3601, Scopulariopsis brevicaulis CGMCC3.3987, Aureobasidium pullulans CGMCC3.837; The test results are as follows:

[0061]

[0062] As can be seen from the data in the above table, by modifying nano-zinc oxide, a rubber based on N,N'-di-sec-butyl-p-phenylenediamine obtained in the present invention has good cold resistance, tear resistance, flame retardancy and mildew resistance.

[0063] In the description of the specification, the description with reference to terms such as "an embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0064] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A rubber based on N,N'-di-sec-butyl-p-phenylenediamine, characterized in that, it is processed from the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 1-5 parts of hydroxyl silicone oil, 1-2 parts of N,N'-di-sec-butyl-p-phenylenediamine, 1-2 parts of hydrogen-containing polysiloxane, 0.2-0.8 part of N-tert-butyl-2-benzothiazole sulfenamide, 0.5-1 part of tricresyl phosphate, 1-3 parts of modified nano zinc oxide; wherein, the modified nano zinc oxide is prepared by the following steps: S1. Put cyanuric chloride and ethanol into a three-necked flask, control the temperature at 0-5°C, stir for 5 min, dissolve 1-nonylamine and triethylamine in ethanol, slowly drip them into the three-necked flask with a constant pressure dropping funnel, continue to react for 3 h after dropping, after the reaction is completed, remove ethanol by rotary evaporation under reduced pressure, wash the solid with 0.5 mol / L dilute hydrochloric acid and saturated brine in turn, and then put it into a vacuum drying oven at 50°C for drying for 6 h to obtain intermediate 1; S2. Add intermediate 1 and pyridine into a three-necked flask, add ethanol as a solvent, control the heating temperature at 80°C, reflux and react for 5 h, remove the solvent by rotary evaporation under reduced pressure after the reaction is completed to obtain intermediate 2; S3. Add intermediate 2 and tetrahydrofuran into a three-necked flask, stir at room temperature for 10 min, dissolve glycine methyl ester and sodium carbonate in tetrahydrofuran, slowly drip them into the three-necked flask with a constant pressure dropping funnel, react at room temperature for 4 h after dropping, after the reaction is completed, remove tetrahydrofuran by rotary evaporation, wash the solid with saturated NaCl aqueous solution for many times, and put it into a vacuum drying oven at 50°C for drying for 8 h to obtain intermediate 3; S4. Add intermediate 3 into a flask equipped with a thermometer and a constant pressure dropping funnel, add ethanol as a solvent, stir for 10 min, drip saturated sodium hydroxide aqueous solution, react for 2 h after dropping, after the reaction is completed, drip 4 mol / L hydrochloric acid until pH = 2.5, react for 30 min, rotary evaporate the reaction solution under reduced pressure, wash the obtained solid with NaCl aqueous solution and deionized water in turn until neutral to obtain intermediate 4; the dosage ratio of intermediate 3, ethanol and saturated sodium hydroxide aqueous solution is 10 g:100 mL:50 mL; S5. Add intermediate 4 and triethylamine into a flask, add DMF as a solvent, add amino-functionalized nano zinc oxide and N,N'-diisopropylcarbodiimide, protect with nitrogen, then ultrasonicate for 15 min, and then react at room temperature for 5 h, after the reaction is completed, centrifuge the reaction solution, wash it with DMF and ethanol aqueous solution for 2-3 times in turn, and finally put the product into a vacuum oven at 50°C for drying for 6 h to obtain modified nano zinc oxide.

2. The rubber based on N,N'-di-sec-butyl-p-phenylenediamine according to claim 1, characterized in that, the dosage ratio of cyanuric chloride, 1-nonylamine and triethylamine in step S1 is 10 g:7.75 g:5.5 g.

3. The rubber based on N,N'-di-sec-butyl-p-phenylenediamine according to claim 1, characterized in that, the dosage ratio of intermediate 1, pyridine and ethanol in step S2 is 10 g:2.7 g:100 mL.

4. A rubber based on N,N'-di-sec-butyl-p-phenylenediamine according to claim 1, characterized in that, in step S3, the dosage ratio of intermediate 2, methyl glycinate, and sodium carbonate is 10 g: 2.6 g: 3.2 g.

5. A rubber based on N,N'-di-sec-butyl-p-phenylenediamine according to claim 1, characterized in that, in step S5, the dosage ratio of intermediate 4, triethylamine, amino-functionalized nano zinc oxide, and N,N'-diisopropylcarbodiimide is 10 g: 2.8 g: 2.6 g: 3.5 g.

6. A method for preparing a rubber based on N,N'-di-sec-butyl-p-phenylenediamine according to claim 1, characterized in that, it comprises the following steps: First step, mix methyl vinyl silicone rubber, hydroxy silicone oil, and modified nano zinc oxide evenly in a kneader, heat-treat at 120 °C for 30 min, after cooling to room temperature, add N,N'-di-sec-butyl-p-phenylenediamine, hydrogen-containing polysiloxane, N-tert-butyl-2-benzothiazole sulfenamide, and tricresyl phosphate, and mix and stir evenly using a planetary mixer; Second step, vulcanize and mold the mixture after mixing by compression molding at 140 °C to obtain a rubber based on N,N'-di-sec-butyl-p-phenylenediamine.

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