Anti-aging material containing modified silica and preparation method thereof

Abstract

This invention relates to the field of polymer materials technology and discloses a modified silica-containing anti-aging material and its preparation method. The preparation method is as follows: polypropylene resin, modified silica, modified alkylphenol, calcium stearate, and antioxidant 1010 are added to a high-speed mixer and mixed for 10-20 minutes to obtain a mixture. Then, the mixture is added to a twin-screw extruder and extruded at 160-180°C and a screw speed of 200-250 rpm. The mixture is then granulated to obtain the modified silica-containing anti-aging material. This invention's anti-aging material not only possesses excellent anti-aging properties but also improves mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a modified silica-containing anti-aging material and its preparation method. Background Technology

[0002] As a daily consumer product, toothpaste packaging tubes are exposed to various storage conditions over long-term use. Repeated squeezing and folding of the tubes in daily life can cause aging issues. Once micro-cracks appear in the inner layer of the tube, external oxygen can easily penetrate, and internal fragrance and moisture can easily escape, leading to loss of flavor, drying out, or spoilage of the toothpaste. Therefore, preventing this phenomenon is key to solving the problem. For example, Chinese patent application CN120484528A discloses a bamboo-based plastic packaging material and its preparation method. This bamboo-based plastic packaging material has good flame retardant, antibacterial, and tensile strength properties, but its anti-aging performance needs improvement. Summary of the Invention

[0003] (a) Technical problems to be solved

[0004] To address the shortcomings of existing technologies, this invention provides a modified silica-containing anti-aging material and its preparation method. The anti-aging material of this invention not only has good anti-aging properties but also improves mechanical properties.

[0005] (II) Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a modified silica anti-aging material comprising the following weight components: 70-90 parts by weight of polypropylene resin, 2-4 parts by weight of modified silica, 1-3 parts by weight of modified alkylphenol, 0.2-0.5 parts by weight of calcium stearate, and 0.3-0.4 parts by weight of antioxidant 1010.

[0007] Furthermore, the method for preparing the modified silica is as follows:

[0008] Step 1: Add nano-silica to deionized water and ultrasonically disperse for 20-30 min. Then add tetraoctylammonium bromide and stir at room temperature for 2-4 h. Next, add 3-aminopropyltriethoxysilane dropwise to the reaction system and reflux at 110-130℃ for 22-26 h. After the reaction is complete, centrifuge, wash, and dry at 100-120℃ for 12-14 h to obtain intermediate 1.

[0009] Step 2: Under nitrogen protection, add erucamide and 3-mercaptopropionic acid to N,N-dimethylformamide solvent, stir and mix, then add benzoin dimethyl ether photoinitiator, and irradiate with 365nm ultraviolet light at 20-40℃ for 3-5 hours. After the reaction is completed, centrifuge, wash and dry to obtain intermediate 2.

[0010] Step 3: Under nitrogen protection, add intermediate 2 to N,N-dimethylformamide solvent, stir until homogeneous, and stir in an ice-water bath for 20-30 min. Then add triethylamine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and intermediate 1, and continue stirring in an ice-water bath for 15-25 min. Finally, add 1-hydroxybenzotriazole dropwise to the reaction system at 0-5℃, and stir at room temperature for 20-30 h. After the reaction is complete, wash and dry to obtain modified silica.

[0011] Furthermore, in step one, the ratio of deionized water, nano-silica, tetraoctylammonium bromide, and 3-aminopropyltriethoxysilane is 50-60 mL: 2-2.06 g: 0.14-0.18 g: 0.08-0.12 g.

[0012] Furthermore, in step two, the ratio of N,N-dimethylformamide, erucamide, 3-mercaptopropionic acid, and dimethyl benzoate is 40-50 mL: 4.82-4.86 g: 1.51-1.55 g: 0.02-0.03 g.

[0013] Further, in step three, the ratio of N,N-dimethylformamide, intermediate 2, triethylamine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, intermediate 1, and 1-hydroxybenzotriazole is 25-30 mL: 2.72-2.76 g: 0.11-0.13 g: 0.46-0.48 g: 1.24-1.28 g: 0.16-0.18 g.

[0014] Further, the modified alkylphenol is prepared by adding 2-tert-butyl-5-epoxypentadecanylphenol and 2,2-di(bromomethyl)-1,3-propanediol to N,N-dimethylformamide solvent, stirring and mixing, then adding a 5 mol / L sodium hydroxide aqueous solution dropwise, stirring and reacting at 40-60℃ for 8-12 h, adding 5% dilute hydrochloric acid dropwise to neutralize after the reaction, removing the solvent by rotary evaporation, filtering, washing and drying to obtain the modified alkylphenol.

[0015] Furthermore, the ratio of N,N-dimethylformamide, 2-tert-butyl-5-epoxypentadecanylphenol, 2,2-di(bromomethyl)-1,3-propanediol, and sodium hydroxide is 35-45 mL: 3.66-3.72 g: 1.61-1.65 g: 2-3 mL.

[0016] Furthermore, the preparation method of the modified silica-containing anti-aging material is as follows: polypropylene resin, modified silica, modified alkylphenol, calcium stearate, and antioxidant 1010 are added to a high-speed mixer and mixed for 10-20 minutes to obtain a mixture. Then, the mixture is added to a twin-screw extruder and extruded at 160-180°C and a screw speed of 200-250 rpm. The mixture is then granulated to obtain the modified silica-containing anti-aging material.

[0017] (iii) Beneficial technical effects

[0018] Nano-silica possesses excellent resistance to ultraviolet aging and can enhance the thermal and oxygen stability and mechanical stability of materials. It is a novel, efficient, multifunctional, and durable anti-aging additive. This invention reacts nano-silica with 3-aminopropyltriethoxysilane to aminate the nano-silica. Subsequently, erucamide is grafted onto the nano-silica using 3-mercaptopropionic acid. Erucamide, as a typical plastic film slip agent, reduces frictional resistance during extrusion and friction, effectively preventing film adhesion and excessive friction between the film and equipment rollers, thus improving production efficiency and material processing efficiency. 2-tert-butyl-5-epoxypentadecanylphenol has a semi-hindered phenolic structure with only one tert-butyl group at the ortho position of the phenolic hydroxyl group, resulting in minimal steric hindrance. This facilitates the inhibition of chain reactions of oxidative free radicals by the phenolic hydroxyl group, thereby enhancing the material's anti-aging ability. Furthermore, the long carbon chain of 2-tert-butyl-5-epoxypentadecanylphenol can entangle and crosslink with polypropylene resin and erucamide to form a molecular crosslinking network, which can effectively toughen the material and significantly improve its mechanical properties. Attached Figure Description

[0019] Figure 1 It is the synthesis reaction formula for intermediate 2. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific embodiments.

[0022] The preparation of 2-tert-butyl-5-epoxypentadecanylphenol was carried out in accordance with the reference "Synthesis and Properties of 2-tert-butyl-5-epoxypentadecanylphenol Antioxidants" (Petroleum Refining & Chemical Engineering, Vol. 52, No. 7, 2021).

[0023] 100g of cashew nut shellac, 8g of formic acid, 0.3g of sulfuric acid, and 200g of hydrogen peroxide were placed in a reactor, stirred, and heated to 70℃ for 3 hours to obtain a brownish-red transparent liquid. The mixture was filtered, washed with 5% KOH solution, and then washed with distilled water until neutral to separate the organic phase. The mixture was then distilled under reduced pressure at 100Pa and 150℃ for 1 hour to remove water and unreacted raw materials to obtain epoxidized cashew nut shellac. 35g of the prepared epoxidized cashew nut shellac was dissolved in 100mL of acetone, and 0.9g of zinc chloride catalyst was added. The mixture was heated and kept at 60℃, and 9.5g of tert-butyl chloride was slowly added dropwise. The reaction was continued for 3 hours to obtain a brownish-red transparent liquid. The mixture was filtered, washed with 5% KOH solution, and then washed with distilled water until neutral. The mixture was then distilled under reduced pressure at 1000Pa and 120℃ for 1 hour to remove solvent, water, and unreacted raw materials to obtain 2-tert-butyl-5-epoxypentadecanylphenol.

[0024] The reagents used in the following specific embodiments are of analytical grade. Additionally:

[0025] Polypropylene powder: grade L5E89, isotacticity 95%, melt flow rate 3g / 10min, manufacturer is China Petroleum Fushun Petrochemical Company;

[0026] Nano-silica: Grade A380, diameter approximately 7nm, specific surface area 350m² 2 / g, manufactured by Aladdin Reagent Co., Ltd.

[0027] Example 1

[0028] (1) Add 2g of nano silica to 50mL of deionized water, sonicate for 20min, then add 0.14g of tetraoctylammonium bromide, stir at room temperature for 2h, then add 0.08g of 3-aminopropyltriethoxysilane dropwise to the reaction system, reflux at 110℃ for 22h, after the reaction is completed, centrifuge, wash, and dry at 100℃ for 12h to obtain intermediate 1;

[0029] (2) Under nitrogen protection, 4.82 g of erucamide and 1.51 g of 3-mercaptopropionic acid were added to 40 mL of N,N-dimethylformamide solvent and stirred. Then, 0.02 g of benzoin dimethyl ether photoinitiator was added and irradiated with 365 nm ultraviolet light at 20 °C for 3 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain intermediate 2.

[0030] (3) Under nitrogen protection, 2.72 g of intermediate 2 was added to 25 mL of N,N-dimethylformamide solvent and stirred evenly. The mixture was stirred for 20 min in an ice-water bath. Then, 0.11 g of triethylamine, 0.46 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1.24 g of intermediate 1 were added. The mixture was stirred for 15 min in an ice-water bath. Finally, 0.16 g of 1-hydroxybenzotriazole was added dropwise to the reaction system at 0 °C. The mixture was stirred at room temperature for 20 h. After the reaction was completed, the mixture was washed and dried to obtain modified silica.

[0031] (4) Add 3.66 g of 2-tert-butyl-5-epoxypentadecanylphenol and 1.61 g of 2,2-di(bromomethyl)-1,3-propanediol to 35 mL of N,N-dimethylformamide solvent, stir and mix, then add 2 mL of sodium hydroxide aqueous solution with a molar concentration of 5 mol / L, stir and react for 8 h at 40 °C, after the reaction is completed, add 5% dilute hydrochloric acid to neutralize, remove the solvent by rotary evaporation, filter, wash and dry to obtain modified alkylphenol;

[0032] (5) 70 parts by weight of polypropylene resin, 2 parts by weight of modified silica, 1 part by weight of modified alkylphenol, 0.2 parts by weight of calcium stearate and 0.3 parts by weight of antioxidant 1010 are added to a high-speed mixer and mixed for 10 minutes to obtain a mixture. Then the mixture is added to a twin-screw extruder and extruded at 160°C and a screw speed of 200 rpm. The mixture is then granulated to obtain an anti-aging material containing modified silica.

[0033] Example 2

[0034] (1) Add 2.06 g of nano silica to 60 mL of deionized water, disperse ultrasonically for 30 min, then add 0.18 g of tetraoctylammonium bromide, stir at room temperature for 4 h, then add 0.12 g of 3-aminopropyltriethoxysilane dropwise to the reaction system, reflux at 130 °C for 26 h, after the reaction is completed, centrifuge, wash, and dry at 120 °C for 14 h to obtain intermediate 1;

[0035] (2) Under nitrogen protection, 4.86 g of erucamide and 1.55 g of 3-mercaptopropionic acid were added to 50 mL of N,N-dimethylformamide solvent and stirred. Then, 0.03 g of benzoin dimethyl ether photoinitiator was added and irradiated with 365 nm ultraviolet light at 40 °C for 5 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain intermediate 2.

[0036] (3) Under nitrogen protection, 2.76 g of intermediate 2 was added to 30 mL of N,N-dimethylformamide solvent and stirred evenly. The mixture was stirred for 30 min in an ice-water bath. Then, 0.13 g of triethylamine, 0.48 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1.28 g of intermediate 1 were added. The mixture was stirred for 25 min in an ice-water bath. Finally, 0.18 g of 1-hydroxybenzotriazole was added dropwise to the reaction system at 5 °C. The mixture was stirred at room temperature for 30 h. After the reaction was completed, the mixture was washed and dried to obtain modified silica.

[0037] (4) Add 3.72 g of 2-tert-butyl-5-epoxypentadecanylphenol and 1.65 g of 2,2-di(bromomethyl)-1,3-propanediol to 45 mL of N,N-dimethylformamide solvent, stir and mix, then add 3 mL of sodium hydroxide aqueous solution with a molar concentration of 5 mol / L, stir and react at 60 °C for 12 h, after the reaction is completed, add 5% dilute hydrochloric acid to neutralize, remove the solvent by rotary evaporation, filter, wash and dry to obtain modified alkylphenol;

[0038] (5) 90 parts by weight of polypropylene resin, 4 parts by weight of modified silica, 3 parts by weight of modified alkylphenol, 0.5 parts by weight of calcium stearate and 0.4 parts by weight of antioxidant 1010 are added to a high-speed mixer and mixed for 20 minutes to obtain a mixture. Then the mixture is added to a twin-screw extruder and extruded at 180°C and a screw speed of 250 rpm. The mixture is then granulated to obtain an anti-aging material containing modified silica.

[0039] Example 3

[0040] (1) Add 2.03 g of nano silica to 55 mL of deionized water, disperse ultrasonically for 25 min, then add 0.16 g of tetraoctylammonium bromide, stir at room temperature for 3 h, then add 0.1 g of 3-aminopropyltriethoxysilane dropwise to the reaction system, reflux at 120 °C for 24 h, after the reaction is completed, centrifuge, wash, and dry at 110 °C for 13 h to obtain intermediate 1;

[0041] (2) Under nitrogen protection, 4.84 g of erucamide and 1.53 g of 3-mercaptopropionic acid were added to 45 mL of N,N-dimethylformamide solvent and stirred. Then, 0.02 g of benzoin dimethyl ether photoinitiator was added and irradiated with 365 nm ultraviolet light at 30 °C for 4 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain intermediate 2.

[0042] (3) Under nitrogen protection, 2.74 g of intermediate 2 was added to 28 mL of N,N-dimethylformamide solvent and stirred evenly. The mixture was stirred for 25 min in an ice-water bath. Then, 0.12 g of triethylamine, 0.47 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1.26 g of intermediate 1 were added. The mixture was stirred for 20 min in an ice-water bath. Finally, 0.17 g of 1-hydroxybenzotriazole was added dropwise to the reaction system at 2 °C. The mixture was stirred at room temperature for 25 h. After the reaction was completed, the mixture was washed and dried to obtain modified silica.

[0043] (4) Add 3.69 g of 2-tert-butyl-5-epoxypentadecanylphenol and 1.63 g of 2,2-di(bromomethyl)-1,3-propanediol to 40 mL of N,N-dimethylformamide solvent, stir and mix, then add 2 mL of sodium hydroxide aqueous solution with a molar concentration of 5 mol / L, stir and react at 50 °C for 10 h, after the reaction is completed, add 5% dilute hydrochloric acid to neutralize, remove the solvent by rotary evaporation, filter, wash and dry to obtain modified alkylphenol;

[0044] (5) 80 parts by weight of polypropylene resin, 3 parts by weight of modified silica, 2 parts by weight of modified alkylphenol, 0.3 parts by weight of calcium stearate and 0.3 parts by weight of antioxidant 1010 are added to a high-speed mixer and mixed for 15 minutes to obtain a mixture. Then the mixture is added to a twin-screw extruder and extruded at 170°C and a screw speed of 220 rpm. The mixture is then granulated to obtain an anti-aging material containing modified silica.

[0045] Example 4

[0046] (1) Add 2.02 g of nano silica to 52 mL of deionized water, sonicate for 22 min, then add 0.15 g of tetraoctylammonium bromide, stir at room temperature for 2 h, then add 0.09 g of 3-aminopropyltriethoxysilane dropwise to the reaction system, reflux at 115 °C for 23 h, after the reaction is completed, centrifuge, wash, and dry at 105 °C for 12 h to obtain intermediate 1;

[0047] (2) Under nitrogen protection, 4.83 g of erucamide and 1.52 g of 3-mercaptopropionic acid were added to 42 mL of N,N-dimethylformamide solvent and stirred. Then, 0.02 g of benzoin dimethyl ether photoinitiator was added and irradiated with 365 nm ultraviolet light at 25 °C for 3 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain intermediate 2.

[0048] (3) Under nitrogen protection, 2.73 g of intermediate 2 was added to 26 mL of N,N-dimethylformamide solvent and stirred until homogeneous. The mixture was stirred for 22 min in an ice-water bath. Then, 0.11 g of triethylamine, 0.47 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1.25 g of intermediate 1 were added. The mixture was stirred for 18 min in an ice-water bath. Finally, 0.16 g of 1-hydroxybenzotriazole was added dropwise to the reaction system at 1 °C. The mixture was stirred at room temperature for 22 h. After the reaction was completed, the mixture was washed and dried to obtain modified silica.

[0049] (4) Add 3.68 g of 2-tert-butyl-5-epoxypentadecanylphenol and 1.62 g of 2,2-di(bromomethyl)-1,3-propanediol to 38 mL of N,N-dimethylformamide solvent, stir and mix, then add 2 mL of sodium hydroxide aqueous solution with a molar concentration of 5 mol / L, stir and react at 45 °C for 9 h, after the reaction is completed, add 5% dilute hydrochloric acid to neutralize, remove the solvent by rotary evaporation, filter, wash and dry to obtain modified alkylphenol;

[0050] (5) 75 parts by weight of polypropylene resin, 2 parts by weight of modified silica, 2 parts by weight of modified alkylphenol, 0.3 parts by weight of calcium stearate and 0.3 parts by weight of antioxidant 1010 are added to a high-speed mixer and mixed for 12 minutes to obtain a mixture. Then the mixture is added to a twin-screw extruder and extruded and granulated at 165°C and a screw speed of 210 rpm to obtain an anti-aging material containing modified silica.

[0051] Example 5

[0052] (1) Add 2.05 g of nano silica to 58 mL of deionized water, disperse ultrasonically for 28 min, then add 0.17 g of tetraoctylammonium bromide, stir at room temperature for 4 h, then add 0.11 g of 3-aminopropyltriethoxysilane dropwise to the reaction system, reflux at 125 °C for 25 h, after the reaction is completed, centrifuge, wash, and dry at 115 °C for 14 h to obtain intermediate 1;

[0053] (2) Under nitrogen protection, 4.85 g of erucamide and 1.54 g of 3-mercaptopropionic acid were added to 48 mL of N,N-dimethylformamide solvent and stirred. Then, 0.03 g of benzoin dimethyl ether photoinitiator was added and irradiated with 365 nm ultraviolet light at 35 °C for 5 h. After the reaction was completed, the mixture was centrifuged, washed and dried to obtain intermediate 2.

[0054] (3) Under nitrogen protection, 2.75 g of intermediate 2 was added to 29 mL of N,N-dimethylformamide solvent and stirred evenly. The mixture was stirred for 28 min in an ice-water bath. Then, 0.13 g of triethylamine, 0.47 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1.27 g of intermediate 1 were added. The mixture was stirred for 22 min in an ice-water bath. Finally, 0.18 g of 1-hydroxybenzotriazole was added dropwise to the reaction system at 3 °C. The mixture was stirred at room temperature for 28 h. After the reaction was completed, the mixture was washed and dried to obtain modified silica.

[0055] (4) Add 3.7 g of 2-tert-butyl-5-epoxypentadecanylphenol and 1.64 g of 2,2-di(bromomethyl)-1,3-propanediol to 42 mL of N,N-dimethylformamide solvent, stir and mix, then add 3 mL of sodium hydroxide aqueous solution with a molar concentration of 5 mol / L, stir and react at 55 °C for 11 h, after the reaction is completed, add 5% dilute hydrochloric acid to neutralize, remove the solvent by rotary evaporation, filter, wash and dry to obtain modified alkylphenol;

[0056] (5) 85 parts by weight of polypropylene resin, 3 parts by weight of modified silica, 3 parts by weight of modified alkylphenol, 0.4 parts by weight of calcium stearate and 0.4 parts by weight of antioxidant 1010 are added to a high-speed mixer and mixed for 18 minutes to obtain a mixture. Then the mixture is added to a twin-screw extruder and extruded and granulated at 175°C and a screw speed of 240 rpm to obtain an anti-aging material containing modified silica.

[0057] Comparative Example 1

[0058] The difference between this comparative example and Example 5 is that nano-silica was used instead of modified silica.

[0059] Comparative Example 2

[0060] The difference between this comparative example and Example 5 is that 2-tert-butyl-5-epoxypentadecanylphenol was used instead of the modified alkylphenol.

[0061] Performance testing:

[0062] Sample preparation: The anti-aging materials obtained in Examples 1-5 and Comparative Examples 1-2 were injection molded to form specimens with dimensions of 100×10×3mm. The specimens were subjected to accelerated UV aging tests according to ASTM G154 Cycle1, with a radiation wavelength of 340nm and an UV radiation intensity of 0.98W / m². 2 The aged samples were obtained by continuous illumination for 1000 hours and blackboard temperature of 50℃.

[0063] (1) Notched impact strength test: The test was conducted according to ISO 179-1:2010 "Determination of impact properties of plastic cylinder supports", with an impact velocity of 3.8 m / s. Five samples were tested in each group, and the average value was taken. The test results are shown in Table 1.

[0064] Table 1: Notched Impact Strength Test

[0065]

[0066] As can be seen from Table 1, the anti-aging materials prepared in Examples 1-5 and Comparative Examples 1-2 have good aging resistance and impact resistance.

[0067] (2) Tensile strength test: The test was conducted in accordance with GB / T 1040.1-2025 "Determination of tensile properties of plastics - Part 1: General". Five samples were tested in each group, and the average value was taken. The test results are shown in Table 2.

[0068] Table 2: Tensile Strength Test

[0069]

[0070] As can be seen from Table 2, the anti-aging materials prepared in Examples 1-5 and Comparative Examples 1-2 have good aging resistance and tensile strength.

[0071] The comparison shows that the anti-aging material samples prepared in Comparative Examples 1-2 exhibited a higher rate of decrease in impact resistance and tensile strength after UV accelerated aging tests compared to the anti-aging material samples prepared in the Examples. This is because the samples prepared in Comparative Example 1, compared to the Examples, did not undergo amination and grafting modification, thus failing to effectively disperse and reinforce the material, which easily leads to stress concentration within the material. In contrast, the samples prepared in Comparative Example 2, compared to the Examples, reduced the semi-hindered phenolic structure component of 2-tert-butyl-5-epoxypentadecanylphenol. This structure is beneficial for the phenolic hydroxyl groups to inhibit the chain reaction of oxidative free radicals in the material, thereby improving the anti-aging ability of the material. Furthermore, the cross-linking strength of the molecular cross-linking network in the samples prepared in Comparative Examples 1-2 was not as strong as that in the Examples, resulting in a decrease in the mechanical properties of the material.

[0072] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0073] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0074] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A modified silica-containing anti-aging material, characterized in that, It includes the following components by weight: 70-90 parts by weight of polypropylene resin, 2-4 parts by weight of modified silica, 1-3 parts by weight of modified alkylphenol, 0.2-0.5 parts by weight of calcium stearate, and 0.3-0.4 parts by weight of antioxidant 1010. The method for preparing the modified silica is as follows: Step 1: Add nano-silica to deionized water and ultrasonically disperse for 20-30 min. Then add tetraoctylammonium bromide and stir at room temperature for 2-4 h. Next, add 3-aminopropyltriethoxysilane dropwise to the reaction system and reflux at 110-130℃ for 22-26 h. After the reaction is complete, centrifuge, wash, and dry at 100-120℃ for 12-14 h to obtain intermediate 1. Step 2: Under nitrogen protection, add erucamide and 3-mercaptopropionic acid to N,N-dimethylformamide solvent, stir and mix, then add benzoin dimethyl ether photoinitiator, and irradiate with 365nm ultraviolet light at 20-40℃ for 3-5 hours. After the reaction is completed, centrifuge, wash and dry to obtain intermediate 2. Step 3: Under nitrogen protection, add intermediate 2 to N,N-dimethylformamide solvent, stir until homogeneous, and stir in an ice-water bath for 20-30 min. Then add triethylamine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and intermediate 1, and continue stirring in an ice-water bath for 15-25 min. Finally, add 1-hydroxybenzotriazole dropwise to the reaction system at 0-5℃, and stir at room temperature for 20-30 h. After the reaction is complete, wash and dry to obtain modified silica. The modified alkylphenol is prepared by adding 2-tert-butyl-5-epoxypentadecanylphenol and 2,2-di(bromomethyl)-1,3-propanediol to N,N-dimethylformamide solvent, stirring and mixing, then adding a 5 mol / L sodium hydroxide aqueous solution dropwise, stirring and reacting at 40-60℃ for 8-12 h, adding 5% dilute hydrochloric acid dropwise to neutralize after the reaction, removing the solvent by rotary evaporation, filtering, washing and drying to obtain the modified alkylphenol.

2. The modified silica-containing anti-aging material according to claim 1, characterized in that, In step one, the ratio of deionized water, nano-silica, tetraoctylammonium bromide, and 3-aminopropyltriethoxysilane is 50-60 mL: 2-2.06 g: 0.14-0.18 g: 0.08-0.12 g.

3. The modified silica-containing anti-aging material according to claim 1, characterized in that, In step two, the ratio of N,N-dimethylformamide, erucamide, 3-mercaptopropionic acid, and dimethyl benzoate is 40-50 mL: 4.82-4.86 g: 1.51-1.55 g: 0.02-0.03 g.

4. The modified silica-containing anti-aging material according to claim 1, characterized in that, In step three, the ratio of N,N-dimethylformamide, intermediate 2, triethylamine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, intermediate 1, and 1-hydroxybenzotriazole is 25-30 mL: 2.72-2.76 g: 0.11-0.13 g: 0.46-0.48 g: 1.24-1.28 g: 0.16-0.18 g.

5. The modified silica-containing anti-aging material according to claim 1, characterized in that, In the preparation method of the modified alkylphenol, the ratio of N,N-dimethylformamide, 2-tert-butyl-5-epoxypentadecanylphenol, 2,2-di(bromomethyl)-1,3-propanediol and sodium hydroxide is 35-45mL:3.66-3.72g:1.61-1.65g:2-3mL.

6. A method for preparing a modified silica-containing anti-aging material as described in any one of claims 1-5, characterized in that, Polypropylene resin, modified silica, modified alkylphenol, calcium stearate, and antioxidant 1010 are added to a high-speed mixer and mixed for 10-20 minutes to obtain a mixture. The mixture is then added to a twin-screw extruder and extruded at 160-180℃ and a screw speed of 200-250 rpm. The mixture is then granulated to obtain an anti-aging material containing modified silica.

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