Migration-resistant macromolecular anti-aging agent as well as preparation method and application thereof

Abstract

The invention discloses a migration-resistant macromolecular anti-aging agent as well as a preparation method and application thereof, and belongs to the technical field of anti-aging agents. The preparation method comprises the following steps: putting p-aminodiphenylamine into a reaction container; heating the reaction container, and stirring the interior of the reaction container by using a stirrer; dropwise adding glycidyl methacrylate into the reaction container; performing constant-temperature reaction for a period of time to obtain a reaction material; adding white carbon black, pouring reaction materials into a barrel of a high-speed stirring dispersion machine, and stirring and mixing; and taking out the powdery product to obtain the migration-resistant macromolecular anti-aging agent. According to the migration-resistant macromolecular anti-aging agent, p-aminodiphenylamine and glycidyl methacrylate serve as raw materials, the macromolecular anti-aging agent containing double bonds and hydroxyl is prepared through amino ring-opening epoxy reaction, the migration resistance of the anti-aging agent can be greatly improved through combination of the carbon-carbon double bonds and the structure on the surface of rubber, meanwhile, the hydroxyl can capture free radicals, and the migration resistance of the anti-aging agent is improved. The aging process of the rubber is delayed and the service life is prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of antioxidants, and in particular relates to a migration-resistant macromolecular antioxidant and a preparation method and application thereof. Background Art

[0002] Tire compounds contain high levels of the antioxidant 6PPD. 6PPD-quinone, formed when 6PPD comes into contact with ozone, is lethal to coho salmon in the ocean. Consequently, existing policies and regulations for tires and vehicles include a series of environmental and safety standards that may indirectly restrict the use of 6PPD, particularly due to the potential harm its degradation product, 6PPD-quinone, poses to aquatic ecosystems. Traditional amine antioxidants, such as 4020 and 4010NA, have low molecular weights and are prone to migration, resulting in blooming or staining on rubber surfaces. This presents a difficult problem for the tire industry. Summary of the Invention

[0003] In order to solve the problems of traditional antioxidants such as high toxicity, easy migration, pollution, and inability to come into contact with food, this application adopts a series of improvement ideas such as increasing molecular weight, improving compatibility, introducing other functional groups, and greening the synthesis process. Ultimately, the traditional 4020 antioxidant is improved by macromolecularization, functionalization, sustained release, loading, and greening, thereby obtaining a migration-resistant macromolecular antioxidant.

[0004] In order to achieve the above object, the technical solution adopted by the present invention is: a method for preparing a migration-resistant macromolecular antioxidant, comprising the following steps: S1. Weigh a certain amount of p-aminodiphenylamine and put it into a reaction container; S2. Heating the reaction vessel to a certain temperature and stirring the interior of the reaction vessel with a stirrer until the p-aminodiphenylamine is completely melted; S3, slowly adding a certain amount of glycidyl methacrylate dropwise into the reaction vessel; S4. After the glycidyl methacrylate is added dropwise, the reaction is continued at a constant temperature for a period of time to obtain a reaction mass; S5. Add a certain amount of white carbon black into the cylinder of the high-speed stirring disperser, pour the reaction materials into the cylinder of the high-speed stirring disperser, and stir and mix at a certain temperature for a period of time; S6. Take out the powdered product from the cylinder of the high-speed stirring disperser to obtain a migration-resistant macromolecular antioxidant.

[0005] As a preferred embodiment of the above technical solution, the weight ratio of glycidyl methacrylate to p-aminodiphenylamine in S3 is 0.1-3.0:1, and the weight ratio of white carbon black to the reaction material in S5 is 0.5-2.0:1.

[0006] As a preferred embodiment of the above technical solution, in S2, the reaction vessel is placed in an oil bath for heating at a temperature of 90-110° C., and the heating temperature is controlled to 90-95° C. after the aminodiphenylamine is completely melted.

[0007] As a preferred embodiment of the above technical solution, the heating temperature is 90-100° C. during the slow dropwise addition of glycidyl methacrylate in S3, and after the dropwise addition of glycidyl methacrylate in S4 is completed, the reaction is carried out at a constant temperature of 90-100° C. for 2 hours.

[0008] As a preferred embodiment of the above technical solution, the feeding temperature of the reaction material in S5 is 90-100°C, and the reaction material and white carbon black are stirred and mixed in the cylinder of a high-speed stirring disperser at a temperature of 50-55°C and a speed of 750-800 rpm for 5-10 minutes.

[0009] The migration-resistant macromolecular antioxidant is prepared by the above-mentioned preparation method.

[0010] The application of the migration-resistant macromolecular antioxidant is to use the migration-resistant macromolecular antioxidant as a raw material for rubber production.

[0011] As a preferred embodiment of the above technical solution, the rubber is used to produce tires.

[0012] The reaction process of glycidyl methacrylate and p-aminodiphenylamine is as follows: .

[0013] The beneficial effects of the present invention are as follows: the migration-resistant macromolecular antioxidant of the present application is prepared from p-aminodiphenylamine and glycidyl methacrylate through an amino ring-opening epoxy reaction to obtain a macromolecular antioxidant containing double bonds and hydroxyl groups, wherein the carbon-carbon double bond is combined with the structure of the rubber surface, which can greatly improve the migration resistance of the antioxidant. At the same time, the hydroxyl groups can capture free radicals, delay the aging process of the rubber, and extend the service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 Schematic diagram of the mechanism of action of the migration-resistant macromolecular antioxidant of the present invention; Figure 2 1 is a graph showing the performance test results of the rubber products prepared in each embodiment. DETAILED DESCRIPTION

[0015] The technical solution of the present invention will be described clearly and completely below. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0016] Example 1 S1. Weigh 129.6 g of p-aminodiphenylamine and place it into a reaction vessel; S2. Heat the reaction vessel to 100° C. and stir the interior of the reaction vessel with a stirrer until the p-aminodiphenylamine is completely melted, then cool the reaction vessel to 90° C. S3. Slowly add 129.6 g of glycidyl methacrylate dropwise into the reaction vessel, controlling the temperature in the reaction vessel at about 90° C. S4, after the glycidyl methacrylate was added dropwise, the mixture was reacted at 90° C. for 2 h to obtain a reaction mass; S5. Add 320g of white carbon black into the cylinder of the high-speed stirring disperser, pour the reaction material into the cylinder of the high-speed stirring disperser while it is still hot, and stir and mix at a temperature of about 50°C and a speed of 750-800rpm for 5-10min; S6. Take out the gray powder product in the cylinder of the high-speed stirring disperser to obtain a migration-resistant macromolecular antioxidant.

[0017] The prepared migration-resistant macromolecular antioxidant is used as a raw material for rubber production: 3 parts of migration-resistant macromolecular antioxidant, 100 parts of styrene-butadiene rubber, 70 parts of white carbon black, 20 parts of softener, 5 parts of accelerator, etc., and rubber products for tire production are obtained through mixing, calendering, molding, vulcanization and other processes.

[0018] Example 2 S1. Weigh 129.6 g of p-aminodiphenylamine and place it into a reaction vessel; S2. Heat the reaction vessel to 100° C. and stir the interior of the reaction vessel with a stirrer until the p-aminodiphenylamine is completely melted, then cool the reaction vessel to 90° C. S3. Slowly add 80 g of glycidyl methacrylate dropwise into the reaction vessel, and control the temperature in the reaction vessel at about 90° C. S4, after the glycidyl methacrylate was added dropwise, the mixture was reacted at 90° C. for 2 h to obtain a reaction mass; S5. Add 210 g of white carbon black into the cylinder of a high-speed stirring disperser, pour the reaction material into the cylinder of the high-speed stirring disperser while it is still hot, and stir and mix at a temperature of about 50° C. and a speed of 750-800 rpm for 5-10 minutes; S6. Take out the gray powder product in the cylinder of the high-speed stirring disperser to obtain a migration-resistant macromolecular antioxidant.

[0019] The prepared migration-resistant macromolecular antioxidant is used as a raw material for rubber production: 3 parts of migration-resistant macromolecular antioxidant, 100 parts of styrene-butadiene rubber, 70 parts of white carbon black, 20 parts of softener, 5 parts of accelerator, etc., and rubber products for tire production are obtained through mixing, calendering, molding, vulcanization and other processes.

[0020] Comparative Example 1 3 parts of 4020, 100 parts of styrene-butadiene rubber, 70 parts of white carbon black, 20 parts of softener, 5 parts of accelerator, etc. are obtained through mixing, calendering, molding, vulcanization and other processes to produce rubber products for tire production.

[0021] The rubber products prepared in the above examples and comparative examples were tested for performance: samples of the same mass were placed in the same mass of ethanol and soaked for 10 days to observe the color change. Figure 2 As shown, after ethanol soaking, the color of Comparative Example 1 is the darkest, and the antioxidant migrates the most, while the colors of Examples 1 and 2 are the lightest, and the migration resistance effect is better.

[0022] It is worth mentioning that the technical features such as the high-speed stirring disperser involved in the patent application of this invention should be regarded as prior art. The specific structure, working principle and possible control method and spatial layout method of these technical features can be selected by conventional means in the field and should not be regarded as the inventive point of this patent. This patent will not be further elaborated.

[0023] The above describes in detail the preferred specific embodiments of the present invention. It should be understood that ordinary technicians in this field can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solutions that can be obtained by technicians in this technical field through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of existing technologies should be within the scope of protection determined by the claims.

Claims

1. A method for preparing a migration-resistant macromolecular antioxidant, characterized in that: The following steps are included: S1. Weigh a certain amount of p-aminodiphenylamine and put it into a reaction container; S2. Heating the reaction vessel to a certain temperature and stirring the interior of the reaction vessel with a stirrer until the p-aminodiphenylamine is completely melted; S3, slowly adding a certain amount of glycidyl methacrylate dropwise into the reaction vessel; S4. After the glycidyl methacrylate is added dropwise, the reaction is continued at a constant temperature for a period of time to obtain a reaction mass; S5. Add a certain amount of white carbon black into the cylinder of the high-speed stirring disperser, pour the reaction materials into the cylinder of the high-speed stirring disperser, and stir and mix at a certain temperature for a period of time; S6. Take out the powdered product from the cylinder of the high-speed stirring disperser to obtain a migration-resistant macromolecular antioxidant.

2. The method for preparing the migration-resistant macromolecular antioxidant according to claim 1, wherein The weight ratio of glycidyl methacrylate to p-aminodiphenylamine in S3 is: 0.1-3.0:1, and the weight ratio of white carbon black to reaction materials in S5 is 0.5-2.0:

1.

3. The preparation method of the migration-resistant macromolecular antioxidant as claimed in claim 1, wherein In S2, the reaction vessel is placed in an oil bath for heating at a temperature of 90-110° C., and the heating temperature is controlled to 90-95° C. after the aminodiphenylamine is completely melted.

4. The preparation method of the migration-resistant macromolecular antioxidant as claimed in claim 1, wherein The heating temperature is 90-100° C. during the slow dropwise addition of glycidyl methacrylate in S3. After the dropwise addition of glycidyl methacrylate in S4 is completed, the reaction is carried out at a constant temperature of 90-100° C. for 2 hours.

5. The method for preparing the migration-resistant macromolecular antioxidant according to claim 1, wherein The feeding temperature of the reaction material in S5 is 90-100° C. The reaction material and white carbon black are stirred and mixed in the cylinder of a high-speed stirring disperser at a temperature of 50-55° C. and a rotation speed of 750-800 rpm for 5-10 minutes.

6. Migration-resistant macromolecular antioxidant, characterized in that: Prepared by the preparation method according to any one of claims 1 to 5.

7. The use of the migration-resistant macromolecular antioxidant as claimed in claim 6, characterized in that: The migration-resistant macromolecular antioxidant is used as a raw material for producing rubber.

8. The use of the migration-resistant macromolecular antioxidant as claimed in claim 7, characterized in that: The rubber is used to produce tires.

Images