Wear-resistant and anti-aging pp material and application thereof

Abstract

The application relates to the technical field of PP material, and discloses a wear-resistant and anti-aging PP material and application thereof; the wear-resistant and anti-aging PP material is prepared by taking PP powder, a diphenyl phosphate base hindered phenol antioxidant component and modified graphene as raw materials, uniformly mixing the raw materials, extruding and granulating, and injection molding to obtain the wear-resistant and anti-aging PP material. An intermediate product C is prepared through a series of reactions; the intermediate product C is reacted with graphene oxide; the graphene oxide is dispersed; an organic-inorganic flame-retardant structure is formed; the intermediate product C is again reacted with beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to obtain a diphenyl phosphate base hindered phenol antioxidant component; the two components are added into the PP material to synergistically improve the wear resistance, anti-aging effect, flame-retardant effect and mechanical property of the PP material; and the PP material has wide application prospects in daily-use plastic products.

Description

Technical Field

[0001] This invention relates to the field of PP material technology, specifically to a wear-resistant and anti-aging PP material and its applications. Background Technology

[0002] Polypropylene (PP) is a high-performance thermoplastic polymer widely used in the automotive, electronics, and packaging industries due to its advantages such as low cost, light weight, and good processability. However, because its molecular structure contains a large number of tertiary hydrocarbon groups, it is prone to degradation under the influence of oxygen, high temperature, and shear force. As a result, everyday plastic products made from PP (such as shelves, storage boxes, tableware, and toys) experience a decline in various properties and ultimately lose their usability. Therefore, to ensure the durability of PP materials, anti-oxidation treatment is essential.

[0003] For example, patent CN 115368673 B discloses a graphene-modified flame-retardant polypropylene material and its preparation method. This invention uses maleic anhydride-grafted polypropylene, modified graphene, flame retardants, etc. as raw materials to prepare a material with good flame-retardant properties. However, in the use of daily plastic products, the anti-aging and wear resistance of PP materials are also important considerations. Summary of the Invention

[0004] (a) Technical problems to be solved

[0005] To address the shortcomings of existing technologies, this invention provides a wear-resistant and anti-aging PP material and its applications. The prepared PP material exhibits good wear resistance, anti-aging effect, flame retardancy, and mechanical properties.

[0006] (II) Technical Solution

[0007] One objective of this invention is to provide a wear-resistant and anti-aging PP material, which is prepared by the following steps:

[0008] S1. Add intermediate product C to ethanol solvent and stir magnetically for 30-40 min. Then add graphene oxide and control the temperature at 85-90℃. Stir and react at this temperature for 32-36 h. After the reaction is complete, wash with deionized water and ethanol sequentially. Dissolve the product in deionized water, sonicate for 2-3 h, filter, and dry to obtain modified graphene. The ratio of intermediate product C to graphene oxide is (0.004-0.008) mol:1 g. In this reaction, oxygen is utilized... The epoxy structure on the surface of graphene undergoes a ring-opening reaction with the amino group in the intermediate product C to obtain modified graphene. Graphene is prone to agglomeration. This invention modifies it to increase the compatibility between PP material and graphene, allowing it to be uniformly dispersed in the material. The uniformly dispersed graphene can not only act as a stress concentration point, absorbing more stress when the PP material is subjected to external stress, but also form a transfer film on the contact surface during the friction process, reducing the coefficient of friction and the wear rate.

[0009] S2. Under nitrogen protection at 0℃, add intermediate product C to acetonitrile solvent and stir until homogeneous. Add β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, followed by 0.2 mol / L triethylamine acetonitrile solution. Control the pH of the reaction system to 9-10, stir for 1-2 hours, raise the temperature to 50-60℃, and react for 22-26 hours. After the reaction is complete, distill under reduced pressure and add dichloromethane. Use 5% of the solution sequentially. Washed with NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution, the product was distilled under reduced pressure, washed with deionized water, and dried to obtain the biphenyl phosphate-based hindered phenolic antioxidant component. The ratio of intermediate product C to β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was 1 mol:(4-4.5) mol. In this reaction, the amino group in intermediate product C undergoes an amidation reaction with β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride to obtain the biphenyl phosphate-based hindered phenolic antioxidant component. The oxygen component, with its star-shaped structure, not only possesses numerous branched chains, but also disperses stress along these chains when added to PP materials under external stress. Furthermore, its numerous rigid benzene ring structures restrict molecular chain movement under stress, thus improving the mechanical properties of PP materials. Moreover, the hindered phenolic structure exhibits excellent antioxidant properties. Introducing the biphenyl phosphate-based hindered phenolic antioxidant component into PP materials can enhance both their mechanical properties and anti-aging properties. The synthetic route is as follows:

[0010]

[0011] S3. Add PP powder, biphenyl phosphate-based hindered phenolic antioxidant component, and modified graphene to a high-speed mixer and mix evenly. Then, place the mixture in a twin-screw extruder for extrusion granulation, and finally place it in an injection molding machine for injection molding to obtain wear-resistant and anti-aging PP material. The ratio of PP powder, biphenyl phosphate-based hindered phenolic antioxidant component, and modified graphene is 100g:(0.5-1)g:(2-6)g.

[0012] Furthermore, in S3, the temperatures of each section of the twin-screw extruder are 180℃, 190℃, 200℃, and 190℃, and the screw speed is 120r / min; the nozzle temperature of the injection molding machine is 220℃, and the injection pressure is 65MPa.

[0013] Furthermore, the preparation method of the intermediate product C includes the following steps:

[0014] (1) Phosphorus oxychloride and 2,2',6,6'-tetrahydroxybiphenyl were added to dichloromethane solvent. Under nitrogen protection, the temperature was controlled at 35-40℃, and the mixture was stirred and dispersed evenly. Triethylamine was then added, and the reaction was allowed to proceed for 3-5 hours. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, rotary evaporated, and dried to obtain intermediate product A. The molar ratio of phosphorus oxychloride, 2,2',6,6'-tetrahydroxybiphenyl, and triethylamine was (2-2.2) mol:1 mol:(4.2-4.4) mol. The synthetic route is as follows:

[0015]

[0016] (2) Intermediate product A, 3,5-dinitroaniline, and triethylamine were added to dichloromethane solvent, stirred and dispersed, and reacted at room temperature for 2-4 hours. After the reaction was completed, the mixture was filtered, washed with ethyl acetate, and dried to obtain intermediate product B. The molar ratio of intermediate product A, 3,5-dinitroaniline, and triethylamine was 1 mol:(2-2.2) mol:(2.2-2.5) mol. The synthetic route is as follows:

[0017]

[0018] (3) Add intermediate product B, SnCl2, and concentrated hydrochloric acid to ethanol solvent, heat to 80-85℃ under magnetic stirring, react for 4-6 hours. After the reaction is complete, cool to room temperature, filter, wash with acetone, dissolve in deionized water, filter, adjust pH to 9-10 with 1mol / L sodium hydroxide solution, filter, and dry to obtain intermediate product C. The ratio of intermediate product B to SnCl2 is 1mol:(18-20)mol. In this reaction, the nitro group in intermediate product B is reduced to obtain intermediate product C. The obtained intermediate product C contains flame-retardant phosphorus and nitrogen. When heated, phosphorus produces phosphoric acid, metaphosphoric acid, and other strong dehydrating substances, which promote the dehydration and carbonization of the material and form a dense film on the surface of the material, hindering the transport of substances and energy transfer. When heated, nitrogen produces flame-retardant gas, which dilutes the content of flammable gases in the air. Therefore, introducing it into PP material can improve the flame retardant performance of PP material. The reaction synthesis route is as follows:

[0019]

[0020] The second objective of this invention is the application of the wear-resistant and anti-aging PP material in daily-use plastic products.

[0021] (III) Beneficial Technical Effects

[0022] This invention prepares an intermediate product C through a series of reactions. This intermediate product C is then reacted sequentially with graphene oxide and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride to obtain modified graphene and a biphenyl phosphate-based hindered phenolic antioxidant component. On one hand, this invention utilizes the flame-retardant elements contained in intermediate product C to form an organic-inorganic synergistic flame-retardant structure with graphene. On the other hand, it utilizes the reaction of intermediate product C with β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride to obtain a star-shaped biphenyl phosphate-based hindered phenolic antioxidant component. This component not only contains the antioxidant hindered phenolic structure, which, when added to the material, enhances its anti-aging properties, but also contains numerous branched structures and rigid benzene ring structures. These, along with the graphene structure, synergistically improve the mechanical properties of the material. Furthermore, the uniformly dispersed graphene can form a transfer film at the contact surface of the PP material during friction, reducing the coefficient of friction, decreasing the wear rate, and improving the material's wear resistance. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. 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.

[0024] Preparation method of graphene oxide: 1.2g of sodium nitrate was added to 46mL of concentrated sulfuric acid, and 1g of flake graphite was added and stirred until homogeneous. Under ice bath conditions, 6g of potassium permanganate was added, the system was heated to 40℃, and stirred for 8h. Then 100mL of water was added, the temperature was raised to 70℃, and the reaction was carried out for 30min. Then 200mL of water and 10mL of hydrogen peroxide were added, and the reaction was carried out for 10min. The mixture was filtered, washed with deionized water until pH=7, and dried to obtain graphene oxide.

[0025] Example 1

[0026] (1) 0.2 mol of phosphorus oxychloride and 0.1 mol of 2,2',6,6'-tetrahydroxybiphenyl were added to dichloromethane solvent. Under nitrogen protection, the temperature was controlled at 40°C. The mixture was stirred and dispersed evenly. 0.42 mol of triethylamine was added to the mixture. The reaction was carried out for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, rotary evaporated, and dried to obtain intermediate product A.

[0027] (2) 80 mmol of intermediate product A, 176 mmol of 3,5-dinitroaniline and 190 mmol of triethylamine were added to dichloromethane solvent, stirred and dispersed, and kept at room temperature for 3 h. After the reaction was completed, the mixture was filtered, washed with ethyl acetate and dried to obtain intermediate product B.

[0028] (3) Add 50 mmol of intermediate product B, 950 mmol of SnCl2 and 200 mL of concentrated hydrochloric acid to ethanol solvent, heat to 85 °C under magnetic stirring, react for 5 h, cool to room temperature after the reaction is completed, filter, wash with acetone, dissolve in deionized water, filter under vacuum, adjust pH to 10 with 1 mol / L sodium hydroxide solution, filter under vacuum, dry to obtain intermediate product C.

[0029] (4) Under nitrogen protection at 0℃, 10 mmol of intermediate product C was added to acetonitrile solvent and stirred until homogeneous. 44 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added to the mixture, followed by 0.2 mol / L of triethylamine acetonitrile solution. The pH of the reaction system was controlled at 9. The mixture was stirred for 2 h, heated to 50℃, and reacted for 26 h. After the reaction was completed, the mixture was distilled under reduced pressure. Dichloromethane was added to the mixture, and it was washed successively with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution. The mixture was then distilled under reduced pressure, washed with deionized water, and dried to obtain the biphenyl phosphate-based hindered phenolic antioxidant component.

[0030] (5) Add 4 mmol of intermediate product C to ethanol solvent, stir magnetically for 35 min, then add 1 g of graphene oxide, control the temperature at 90 °C, stir at constant temperature for 32 h, after the reaction is completed, wash with deionized water and ethanol in sequence, then dissolve the product in deionized water, sonicate for 2 h, filter, dry, and obtain modified graphene.

[0031] (6) Add 100g of PP powder, 0.5g of biphenyl phosphate-based hindered phenol antioxidant component, and 2g of modified graphene to a high-speed mixer and mix evenly. Then place it in a twin-screw extruder for extrusion granulation. The temperature of each section of the twin-screw extruder is 180℃, 190℃, 200℃, and 190℃, and the screw speed is 120r / min. Then place it in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine is 220℃, and the injection pressure is 65MPa to obtain wear-resistant and anti-aging PP material.

[0032] Example 2

[0033] (1) 0.22 mol of phosphorus oxychloride and 0.1 mol of 2,2',6,6'-tetrahydroxybiphenyl were added to dichloromethane solvent. Under nitrogen protection, the temperature was controlled at 35°C. The mixture was stirred and dispersed evenly. 0.44 mol of triethylamine was added to the mixture. The reaction was carried out for 5 h. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, rotary evaporated, and dried to obtain intermediate product A.

[0034] (2) 80 mmol of intermediate product A, 170 mmol of 3,5-dinitroaniline and 180 mmol of triethylamine were added to dichloromethane solvent, stirred and dispersed, and kept at room temperature for 4 h. After the reaction was completed, the mixture was filtered, washed with ethyl acetate and dried to obtain intermediate product B.

[0035] (3) Add 50 mmol of intermediate product B, 1000 mmol of SnCl2 and 200 mL of concentrated hydrochloric acid to ethanol solvent. Stir magnetically and heat to 80 °C for 5 h. After the reaction is complete, cool to room temperature, filter, wash with acetone, dissolve in deionized water, filter under vacuum, adjust pH to 10 with 1 mol / L sodium hydroxide solution, filter under vacuum, and dry to obtain intermediate product C.

[0036] (4) Under nitrogen protection at 0℃, 10 mmol of intermediate product C was added to acetonitrile solvent and stirred until homogeneous. 45 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added, followed by 0.2 mol / L of triethylamine acetonitrile solution. The pH of the reaction system was controlled at 9. The mixture was stirred for 2 h, heated to 60℃, and reacted for 22 h. After the reaction was completed, the mixture was distilled under reduced pressure. Dichloromethane was added to the mixture, and it was washed successively with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution. The mixture was then distilled under reduced pressure, washed with deionized water, and dried to obtain the biphenyl phosphate-based hindered phenolic antioxidant component.

[0037] (5) Add 5 mmol of intermediate product C to ethanol solvent, stir magnetically for 40 min, then add 1 g of graphene oxide, control the temperature at 85 °C, stir at constant temperature for 36 h, after the reaction is completed, wash with deionized water and ethanol in sequence, then dissolve the product in deionized water, sonicate for 2 h, filter, dry, and obtain modified graphene.

[0038] (6) Add 100g of PP powder, 0.6g of biphenyl phosphate-based hindered phenol antioxidant component, and 3g of modified graphene to a high-speed mixer and mix evenly. Then place it in a twin-screw extruder for extrusion granulation. The temperature of each section of the twin-screw extruder is 180℃, 190℃, 200℃, and 190℃, and the screw speed is 120r / min. Then place it in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine is 220℃, and the injection pressure is 65MPa to obtain wear-resistant and anti-aging PP material.

[0039] Example 3

[0040] (1) 0.21 mol of phosphorus oxychloride and 0.1 mol of 2,2',6,6'-tetrahydroxybiphenyl were added to dichloromethane solvent. Under nitrogen protection, the temperature was controlled at 40°C. The mixture was stirred and dispersed evenly. 0.43 mol of triethylamine was added to the mixture. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, rotary evaporated, and dried to obtain intermediate product A.

[0041] (2) 80 mmol of intermediate product A, 160 mmol of 3,5-dinitroaniline and 176 mmol of triethylamine were added to dichloromethane solvent, stirred and dispersed, and kept at room temperature for 4 h. After the reaction was completed, the mixture was filtered, washed with ethyl acetate and dried to obtain intermediate product B.

[0042] (3) Add 50 mmol of intermediate product B, 1000 mmol of SnCl2 and 200 mL of concentrated hydrochloric acid to ethanol solvent. Under magnetic stirring, heat to 85 °C and react for 6 h. After the reaction is completed, cool to room temperature, filter, wash with acetone, dissolve in deionized water, filter under vacuum, adjust pH to 9 with 1 mol / L sodium hydroxide solution, filter under vacuum, dry to obtain intermediate product C.

[0043] (4) Under nitrogen protection at 0℃, 10 mmol of intermediate product C was added to acetonitrile solvent and stirred until homogeneous. 40 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added, followed by 0.2 mol / L triethylamine acetonitrile solution. The pH of the reaction system was controlled at 10. The mixture was stirred for 1 h, heated to 55℃, and reacted for 24 h. After the reaction was completed, the mixture was distilled under reduced pressure. Dichloromethane was added to the mixture, and it was washed successively with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution. The mixture was then distilled under reduced pressure, washed with deionized water, and dried to obtain the biphenyl phosphate-based hindered phenolic antioxidant component.

[0044] (5) Add 6 mmol of intermediate product C to ethanol solvent, stir magnetically for 40 min, then add 1 g of graphene oxide, control the temperature at 90 °C, stir at constant temperature for 34 h, after the reaction is completed, wash with deionized water and ethanol in sequence, then dissolve the product in deionized water, sonicate for 3 h, filter, dry to obtain modified graphene.

[0045] (6) Add 100g of PP powder, 0.7g of biphenyl phosphate-based hindered phenol antioxidant component, and 4g of modified graphene to a high-speed mixer and mix evenly. Then place it in a twin-screw extruder for extrusion granulation. The temperature of each section of the twin-screw extruder is 180℃, 190℃, 200℃, and 190℃, and the screw speed is 120r / min. Then place it in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine is 220℃, and the injection pressure is 65MPa to obtain wear-resistant and anti-aging PP material.

[0046] Example 4

[0047] (1) 0.2 mol of phosphorus oxychloride and 0.1 mol of 2,2',6,6'-tetrahydroxybiphenyl were added to dichloromethane solvent. Under nitrogen protection, the temperature was controlled at 40°C. The mixture was stirred and dispersed evenly. 0.44 mol of triethylamine was added to the mixture. The reaction was carried out for 4 h. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, rotary evaporated, and dried to obtain intermediate product A.

[0048] (2) 80 mmol of intermediate product A, 170 mmol of 3,5-dinitroaniline and 190 mmol of triethylamine were added to dichloromethane solvent, stirred and dispersed, and kept at room temperature for 2 h. After the reaction was completed, the mixture was filtered, washed with ethyl acetate and dried to obtain intermediate product B.

[0049] (3) Add 50 mmol of intermediate product B, 1000 mmol of SnCl2 and 200 mL of concentrated hydrochloric acid to ethanol solvent, heat to 80 °C under magnetic stirring, react for 6 h, cool to room temperature after the reaction is completed, filter, wash with acetone, dissolve in deionized water, filter under vacuum, adjust pH to 10 with 1 mol / L sodium hydroxide solution, filter under vacuum, dry to obtain intermediate product C.

[0050] (4) Under nitrogen protection at 0℃, 10 mmol of intermediate product C was added to acetonitrile solvent and stirred until homogeneous. 45 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added, followed by 0.2 mol / L of triethylamine acetonitrile solution. The pH of the reaction system was controlled at 10. The mixture was stirred for 1 h, heated to 55℃, and reacted for 26 h. After the reaction was completed, the mixture was distilled under reduced pressure. Dichloromethane was added to the mixture, and it was washed successively with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution. The mixture was then distilled under reduced pressure, washed with deionized water, and dried to obtain the biphenyl phosphate-based hindered phenolic antioxidant component.

[0051] (5) 7 mmol of intermediate product C was added to ethanol solvent and magnetically stirred for 35 min. Then 1 g of graphene oxide was added and the temperature was controlled at 90 °C. The reaction was stirred at a constant temperature for 34 h. After the reaction was completed, the product was washed with deionized water and ethanol in sequence. The product was then dissolved in deionized water, ultrasonically treated for 2 h, filtered, and dried to obtain modified graphene.

[0052] (6) Add 100g of PP powder, 0.8g of biphenyl phosphate-based hindered phenol antioxidant component, and 5g of modified graphene to a high-speed mixer and mix evenly. Then place it in a twin-screw extruder for extrusion granulation. The temperature of each section of the twin-screw extruder is 180℃, 190℃, 200℃, and 190℃, and the screw speed is 120r / min. Then place it in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine is 220℃, and the injection pressure is 65MPa to obtain wear-resistant and anti-aging PP material.

[0053] Example 5

[0054] (1) 0.22 mol of phosphorus oxychloride and 0.1 mol of 2,2',6,6'-tetrahydroxybiphenyl were added to dichloromethane solvent. Under nitrogen protection, the temperature was controlled at 40°C. The mixture was stirred and dispersed evenly. 0.43 mol of triethylamine was added to the mixture. The reaction was carried out for 4 h. After the reaction was completed, the mixture was cooled to room temperature, washed with deionized water, rotary evaporated, and dried to obtain intermediate product A.

[0055] (2) 80 mmol of intermediate product A, 176 mmol of 3,5-dinitroaniline and 00 mmol of triethylamine were added to dichloromethane solvent, stirred and dispersed, and kept at room temperature for 3 h. After the reaction was completed, the mixture was filtered, washed with ethyl acetate and dried to obtain intermediate product B.

[0056] (3) Add 50 mmol of intermediate product B, 900 mmol of SnCl2 and 200 mL of concentrated hydrochloric acid to ethanol solvent, heat to 85 °C under magnetic stirring, react for 5 h, cool to room temperature after the reaction is completed, filter, wash with acetone, dissolve in deionized water, filter under vacuum, adjust pH to 9 with 1 mol / L sodium hydroxide solution, filter under vacuum, dry to obtain intermediate product C.

[0057] (4) Under nitrogen protection at 0℃, 10 mmol of intermediate product C was added to acetonitrile solvent and stirred until homogeneous. 40 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added, followed by 0.2 mol / L triethylamine acetonitrile solution. The pH of the reaction system was controlled at 10. The mixture was stirred for 2 h, heated to 55℃, and reacted for 24 h. After the reaction was completed, the mixture was distilled under reduced pressure. Dichloromethane was added to the mixture, and it was washed successively with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution. The mixture was then distilled under reduced pressure, washed with deionized water, and dried to obtain the biphenyl phosphate-based hindered phenolic antioxidant component.

[0058] (5) Add 8 mmol of intermediate product C to ethanol solvent, stir magnetically for 30 min, then add 1 g of graphene oxide, control the temperature at 85 °C, stir at constant temperature for 34 h, after the reaction is completed, wash with deionized water and ethanol in sequence, then dissolve the product in deionized water, sonicate for 3 h, filter, dry, and obtain modified graphene.

[0059] (6) Add 100g of PP powder, 1g of biphenyl phosphate-based hindered phenol antioxidant component and 6g of modified graphene to a high-speed mixer and mix evenly. Then place it in a twin-screw extruder for extrusion granulation. The temperature of each section of the twin-screw extruder is 180℃, 190℃, 200℃ and 190℃, and the screw speed is 120r / min. Then place it in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine is 220℃ and the injection pressure is 65MPa to obtain wear-resistant and anti-aging PP material.

[0060] Comparative Example 1

[0061] The difference between this comparative example and Example 1 is that step (6) does not contain the biphenyl phosphate group hindered phenol antioxidant component.

[0062] Comparative Example 2

[0063] The difference between this comparative example and Example 1 is that step (6) does not contain modified graphene.

[0064] Accelerated aging test: The samples were subjected to accelerated UV aging test according to ASTM G154 Cycle 1, with a radiation wavelength of 340 nm and a UV radiation intensity of 0.98 W / m. 2 Continuous lighting is used, and the blackboard temperature is 50℃.

[0065] According to GB / T1040.1-2006, the tensile strength of the specimen was tested at a tensile rate of 20 mm / min.

[0066] Table 1:

[0067]

[0068]

[0069] As shown in the table, the PP material prepared by this invention has good mechanical properties and anti-aging properties. During the aging process, hydrogen atoms on the PP chain are excited to generate active free radicals, which in turn generate unstable peroxides, leading to the degradation of the PP chain and a decrease in the tensile strength of PP. However, the biphenyl phosphate-based hindered phenolic antioxidant component prepared by this invention contains hindered phenolic structures, which can capture free radicals, reduce the degradation of PP material by free radicals, and improve the mechanical properties after aging.

[0070] The limiting oxygen index of the material was tested using a limiting oxygen index meter.

[0071] Friction and wear tests were conducted using a friction and wear testing machine at room temperature and pressure, with a load of 200 N and a test time of 1 hour.

[0072] Table 2:

[0073]

[0074]

[0075] As shown in the table, the PP material prepared by this invention has good flame retardant effect and wear resistance.

[0076] 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.

Claims

1. A wear resistant and anti-aging PP material, characterized in that, The wear-resistant and anti-aging PP material is prepared by the following steps: S1, the intermediate product C is added to the ethanol solvent, and is stirred magnetically for 30-40 min, then graphene oxide is added thereto, the temperature is controlled to be 85-90 DEG C, and the reaction is stirred at constant temperature for 32-36 h, after the reaction is completed, deionized water and ethanol are used for washing in sequence, then the product is dissolved in deionized water, is subjected to ultrasonic treatment for 2-3 h, is filtered, and is dried to obtain modified graphene, wherein the structural formula of the intermediate product C is: S2, the intermediate product C is added to the acetonitrile solvent under the protection of nitrogen at 0 DEG C, is stirred and mixed uniformly, then beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is added thereto, then 0.2 mol / L triethylamine acetonitrile solution is added thereto, the pH of the reaction system is controlled to be 9-10, is stirred for 1-2 h, is warmed to 50-60 DEG C, and is reacted for 22-26 h, after the reaction is completed, is distilled under reduced pressure, dichloromethane is added thereto, then 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution and saturated NaCl solution are used for washing in sequence, is distilled under reduced pressure, is washed with deionized water, and is dried to obtain a diphenyl phosphate-based hindered phenol antioxidant component; S3, the PP powder, the diphenyl phosphate-based hindered phenol antioxidant component and the modified graphene are added to a high-speed mixer, are mixed uniformly, are placed in a double-screw extruder, are extruded and granulated, are placed in an injection molding machine, and are injection molded to obtain the wear-resistant and anti-aging PP material.

2. The wear resistant and ageing resistant PP material according to claim 1, characterized in that, In the S1, the amount ratio of the intermediate product C to the graphene oxide is (0.004-0.008) mol:1 g.

3. The wear resistant and anti-aging PP material according to claim 1, characterized in that, In the S2, the amount ratio of the intermediate product C to beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1 mol:(4-4.5) mol.

4. The wear resistant and anti-aging PP material according to claim 1, characterized in that, In the S3, the amount ratio of the PP powder to the diphenyl phosphate-based hindered phenol antioxidant component to the modified graphene is 100 g:(0.5-1) g:(2-6) g.

5. The wear resistant and anti-aging PP material according to claim 1, characterized in that, In the S3, in the double-screw extruder, the temperature of each section is 180 DEG C, 190 DEG C, 200 DEG C and 190 DEG C, and the screw rotation speed is 120 r / min; the nozzle temperature of the injection molding machine is 220 DEG C, and the injection pressure is 65 MPa.

6. The wear resistant and anti-aging PP material according to claim 1, characterized in that, The preparation method of the intermediate product C comprises the following steps: (1) phosphorus oxychloride and 2, 2', 6, 6'-tetrahydroxydiphenyl are added to dichloromethane solvent, stirring is performed under the protection of nitrogen, the temperature is controlled to be 35-40 DEG C, triethylamine is added thereto, the reaction is performed for 3-5 h, after the reaction is completed, is cooled to room temperature, is washed with deionized water, is rotary evaporated, and is dried to obtain the intermediate product A; (2) the intermediate product A, 3, 5-dinitroaniline and triethylamine are added to dichloromethane solvent, stirring is performed for dispersion, the reaction is performed at room temperature for 2-4 h, after the reaction is completed, is filtered, is washed with ethyl acetate, and is dried to obtain the intermediate product B; (3) Intermediate product B, SnCl2, concentrated hydrochloric acid are added into ethanol solvent, under magnetic stirring, temperature is raised to 80-85℃, reaction is carried out for 4-6h, after reaction is completed, temperature is cooled to room temperature, filtration is carried out, washing is carried out with acetone, then it is dissolved in deionized water, filtration is carried out, pH is adjusted to 9-10 by using 1mol / L sodium hydroxide solution, filtration is carried out, drying is carried out, intermediate product C is obtained.

7. The wear resistant and ageing resistant PP material according to claim 6, characterized in that, In the (1), the amount of phosphorus oxychloride, 2,2',6,6'-tetrahydroxy diphenyl, triethylamine is (2-2.2) mol:1 mol:(4.2-4.4) mol.

8. The wear resistant and anti-aging PP material according to claim 6, characterized in that, In the (2), the amount of intermediate product A, 3,5-dinitroaniline, triethylamine is 1 mol:(2-2.2) mol:(2.2-2.5) mol.

9. The wear resistant and anti-aging PP material according to claim 6, characterized in that, In the (3), the amount of intermediate product B, SnCl2 is 1 mol:(18-20) mol.

10. The application of the wear-resistant and anti-aging PP material of claim 1 in daily plastic products.

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