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

Abstract

The invention relates to the technical field of PP materials, and discloses a wear-resistant and anti-aging PP material and application thereof.The wear-resistant and anti-aging PP material is obtained by taking PP powder, a biphenyl phosphate hindered phenol antioxidant component and modified graphene as raw materials through uniform mixing, extrusion granulation and injection molding. An intermediate product C is prepared through a series of reactions, the intermediate product C reacts with graphene oxide, graphene oxide is dispersed, an organic-inorganic flame-retardant structure is formed, the intermediate product C reacts with beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, and the flame-retardant performance of the graphene oxide is improved. The biphenyl phosphate-based hindered phenol antioxidant component and the biphenyl phosphate-based hindered phenol antioxidant component are added into the PP material to synergistically improve the wear resistance, the anti-aging effect, the flame-retardant effect and the mechanical property of the PP material, so that the PP material has a wide application prospect in daily plastic products.

Description

Technical Field

[0001] The present invention relates to the technical field of PP materials, in particular to a wear-resistant and aging-resistant PP material and application thereof. Background Art

[0002] Polypropylene (PP) is a high-performance thermoplastic polymer widely used in the automotive, electronics, and packaging industries. It offers advantages such as low cost, light weight, and good processability. However, due to the presence of numerous tertiary hydrocarbon groups in its molecular structure, it is susceptible to degradation under the influence of factors such as oxygen, high temperature, and shear forces. As a result, the performance of everyday plastic products made from it (such as shelves, storage boxes, tableware, and toys) deteriorates, ultimately rendering them useless. Therefore, to ensure the durability of PP materials, they must be treated with antioxidants.

[0003] For example, patent publication number CN 115368673 B discloses a graphene-modified flame-retardant polypropylene material and its preparation method. Using maleic anhydride-grafted polypropylene, modified graphene, and a flame retardant as raw materials, the resulting material exhibits excellent flame retardancy. However, the aging resistance and wear resistance of PP materials are also important in the use of everyday plastic products. Summary of the Invention

[0004] (1) Technical problems solved

[0005] In view of the deficiencies of the prior art, the present invention provides a wear-resistant and aging-resistant PP material and its application. The prepared PP material has good wear resistance, anti-aging effect, flame retardant effect and mechanical properties.

[0006] (2) Technical solution

[0007] One of the purposes of the present invention is to provide a wear-resistant and aging-resistant PP material, wherein the wear-resistant and aging-resistant PP material is prepared by the following steps:

[0008] S1. Add the intermediate product C to an ethanol solvent, stir magnetically for 30-40 minutes, then add graphene oxide thereto, control the temperature to 85-90°C, stir at constant temperature for 32-36 hours, and after the reaction, wash with deionized water and ethanol in turn, then dissolve the product in deionized water, ultrasonically treat for 2-3 hours, filter, and dry to obtain modified graphene, wherein the amount ratio of the intermediate product C to the graphene oxide is (0.004-0.008) mol: 1g. In this reaction, oxygen is used. The epoxy structure contained in the surface of the modified graphene undergoes a ring-opening reaction with the amino group contained in the intermediate product C to obtain modified graphene. The graphene is easy to agglomerate. The present invention modifies it, which can increase the compatibility of the PP material and the graphene, and make it uniformly dispersed in the material. The uniformly dispersed graphene can not only serve as a stress concentration point to absorb 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 of the material, thereby reducing the friction coefficient and the wear rate.

[0009] S2, at 0 ° C, under nitrogen protection, add the intermediate product C to the acetonitrile solvent, stir and mix evenly, add β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, and then add 0.2 mol / L triethylamine acetonitrile solution, control the pH of the reaction system to 9-10, stir for 1-2 hours, heat to 50-60 ° C, react for 22-26 hours, and after the reaction is completed, distill under reduced pressure, add dichloromethane, and use 5% The product was washed with NaHCO3 solution, 0.5 mol / L hydrochloric acid solution and saturated NaCl solution, distilled under reduced pressure, washed with deionized water and dried to obtain a biphenyl phosphate-based hindered phenol antioxidant component, wherein the amount ratio of the intermediate product C and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride was 1 mol:(4-4.5) mol. In this reaction, the amino group contained in the intermediate product C was subjected to an amidation reaction with β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to obtain a biphenyl phosphate-based hindered phenol antioxidant component. The oxygen component is a star-shaped structure with more branched chains. When added to the PP material, the stress can be dispersed along the branched chains when the material is subjected to external stress. It also contains more rigid benzene ring structures, which can limit the movement of molecular segments when subjected to external stress, thereby improving the mechanical properties of the PP material. Moreover, the hindered phenol structure contained therein has excellent antioxidant properties. Introducing the biphenyl phosphate-based hindered phenol antioxidant component into the PP material can improve the mechanical properties and anti-aging properties of the PP material. The reaction synthesis route is as follows:

[0010]

[0011] S3. Add PP powder, biphenyl phosphate-based hindered phenol antioxidant component, and modified graphene to a high-speed mixer, mix well, place in a twin-screw extruder, extrude into granules, and then place in an injection molding machine for injection molding to obtain a wear-resistant and anti-aging PP material. The amount ratio of PP powder, biphenyl phosphate-based hindered phenol antioxidant component, and modified graphene is 100g: (0.5-1)g: (2-6)g

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

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

[0014] (1) Phosphorus oxychloride and 2,2',6,6'-tetrahydroxybiphenyl are added to a dichloromethane solvent, and under nitrogen protection, the temperature is controlled at 35-40°C, and the mixture is stirred and dispersed uniformly. Triethylamine is added thereto, and the mixture is reacted for 3-5 hours. After the reaction is completed, the mixture is cooled to room temperature, washed with deionized water, rotary evaporated, and dried to obtain an intermediate product A, wherein the amount ratio of phosphorus oxychloride, 2,2',6,6'-tetrahydroxybiphenyl, and triethylamine is (2-2.2) mol: 1 mol: (4.2-4.4) mol. The reaction synthesis route is:

[0015]

[0016] (2) Add the intermediate product A, 3,5-dinitroaniline, and triethylamine to a dichloromethane solvent, stir and disperse, and keep the mixture warm for 2-4 hours at room temperature. After the reaction is completed, filter, wash with ethyl acetate, and dry to obtain the intermediate product B. The ratio of the intermediate product A, 3,5-dinitroaniline, and triethylamine is 1 mol: (2-2.2) mol: (2.2-2.5) mol. The reaction synthesis route is:

[0017]

[0018] (3) Add the intermediate product B, SnCl2, and concentrated hydrochloric acid to an ethanol solvent, and heat to 80-85°C under magnetic stirring. React for 4-6 hours. After the reaction is completed, cool to room temperature, filter, wash with acetone, and then dissolve it in deionized water. Filter with suction, adjust the pH to 9-10 with 1 mol / L sodium hydroxide solution, filter with suction, and dry to obtain an intermediate product C. The amount ratio of the intermediate product B to SnCl2 is 1 mol:(18-20) mol. In this reaction, the nitro group in the intermediate product B is reduced to obtain the intermediate product C. The intermediate product C contains flame retardant phosphorus and nitrogen. The phosphorus element generates strong dehydrating substances such as phosphoric acid and metaphosphoric acid when heated, which promotes the dehydration of the material into carbon and forms a dense film on the surface of the material, which hinders material transport and energy transfer. The nitrogen element generates refractory gas when heated, which dilutes the content of flammable gas in the air. Therefore, introducing it into the PP material can improve the flame retardant properties of the PP material. The reaction synthesis route is:

[0019]

[0020] The second purpose of the present invention is to use the wear-resistant and aging-resistant PP material in daily plastic products.

[0021] (3) Beneficial technical effects

[0022] The present invention prepares an intermediate product C through a series of reactions, which is 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 phenol antioxidant component. On the one hand, the present invention utilizes the flame retardant elements contained in the intermediate product C to form an organic-inorganic synergistic flame retardant structure with graphene. On the other hand, the intermediate product C is reacted with β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to obtain a star-shaped biphenyl phosphate-based hindered phenol antioxidant component, which not only contains an antioxidant hindered phenol structure. When added to a material, it can improve the material's anti-aging properties. It also contains a large number of branched structures and rigid benzene ring structures. Both of these structures synergistically improve the material's mechanical properties with the graphene structure. In addition, when the PP material is subjected to friction, the evenly dispersed graphene can form a transfer film on the contact surface, reducing the friction coefficient, reducing the wear rate, and improving the material's wear resistance. DETAILED DESCRIPTION

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in 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 part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0024] Preparation method of graphene oxide: add 1.2g sodium nitrate to 46mL concentrated sulfuric acid, add 1g flake graphite thereto and stir and mix evenly, add 6g potassium permanganate under ice bath conditions, heat the system to 40°C, stir and react for 8h, then add 100mL water thereto, heat to 70°C, react for 30min, then add 200mL water and 10mL hydrogen peroxide, react for 10min, filter, wash with deionized water to pH=7, and dry 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, and the temperature was controlled at 40°C under nitrogen protection. The mixture was stirred and dispersed uniformly. 0.42 mol of triethylamine was added thereto and 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 warm for 3 hours at room temperature. After the reaction was completed, the mixture was filtered, washed with ethyl acetate, and dried to obtain intermediate product B.

[0028] (3) 50 mmol of intermediate product B, 950 mmol of SnCl2, and 200 mL of concentrated hydrochloric acid were added to an ethanol solvent, heated to 85°C under magnetic stirring, and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with acetone, and then dissolved in deionized water, filtered, and the pH was adjusted to 10 using 1 mol / L sodium hydroxide solution. The mixture was filtered and dried to obtain intermediate product C.

[0029] (4) At 0°C and under nitrogen protection, 10 mmol of the intermediate product C was added to an acetonitrile solvent and stirred to mix evenly. 44 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added thereto, and then 0.2 mol / L of triethylamine acetonitrile solution was added thereto. The pH of the reaction system was controlled to be 9, and the mixture was stirred for 2 h. The mixture was heated to 50°C and reacted for 26 h. After the reaction was completed, the mixture was distilled under reduced pressure, and dichloromethane was added thereto. The mixture was washed with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution in sequence. The mixture was distilled under reduced pressure, washed with deionized water, and dried to obtain a biphenyl phosphate-based hindered phenol antioxidant component.

[0030] (5) 4 mmol of intermediate product C was added to ethanol solvent and magnetically stirred for 35 min. Then 1 g of graphene oxide was added thereto. The temperature was controlled at 90 °C and the reaction was stirred at constant temperature for 32 h. After the reaction was completed, deionized water and ethanol were used for washing in sequence. The product was then dissolved in deionized water, ultrasonically treated for 2 h, filtered, and dried to obtain modified graphene.

[0031] (6) 100 g of PP powder, 0.5 g of biphenyl phosphate-based hindered phenol antioxidant component, and 2 g of modified graphene were added to a high-speed mixer and mixed evenly. The mixture was then placed in a twin-screw extruder for extrusion granulation. The temperatures of each section of the twin-screw extruder were 180°C, 190°C, 200°C, and 190°C, and the screw speed was 120 r / min. The mixture was then placed in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine was 220°C, and the injection pressure was 65 MPa to obtain a wear-resistant and aging-resistant 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, and the temperature was controlled at 35°C under nitrogen protection. The mixture was stirred and dispersed uniformly. 0.44 mol of triethylamine was added thereto and the reaction was carried out for 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.

[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 warm for 4 hours at room temperature. After the reaction was completed, the mixture was filtered, washed with ethyl acetate, and dried to obtain intermediate product B.

[0035] (3) 50 mmol of intermediate product B, 1000 mmol of SnCl2, and 200 mL of concentrated hydrochloric acid were added to an ethanol solvent, heated to 80°C under magnetic stirring, and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with acetone, and then dissolved in deionized water. The mixture was filtered and the pH was adjusted to 10 using 1 mol / L sodium hydroxide solution. The mixture was filtered and dried to obtain intermediate product C.

[0036] (4) At 0°C and under nitrogen protection, 10 mmol of the intermediate product C was added to an acetonitrile solvent and stirred to mix evenly. 45 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added thereto, and then 0.2 mol / L of triethylamine acetonitrile solution was added thereto. The pH of the reaction system was controlled to be 9, and the mixture was stirred for 2 h. The mixture was heated to 60°C and reacted for 22 h. After the reaction was completed, the mixture was distilled under reduced pressure, and dichloromethane was added thereto. The mixture was washed with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution in sequence. The mixture was distilled under reduced pressure, washed with deionized water, and dried to obtain a biphenyl phosphate-based hindered phenol antioxidant component.

[0037] (5) 5 mmol of intermediate product C was added to ethanol solvent and magnetically stirred for 40 min. Then 1 g of graphene oxide was added thereto. The temperature was controlled at 85 °C and the reaction was stirred at constant temperature for 36 h. After the reaction was completed, deionized water and ethanol were used for washing in sequence. The product was then dissolved in deionized water, ultrasonically treated for 2 h, filtered, and dried to obtain modified graphene.

[0038] (6) 100 g of PP powder, 0.6 g of biphenyl phosphate-based hindered phenol antioxidant component, and 3 g of modified graphene were added to a high-speed mixer and mixed evenly. The mixture was then placed in a twin-screw extruder for extrusion granulation. The temperatures of each section of the twin-screw extruder were 180°C, 190°C, 200°C, and 190°C, and the screw speed was 120 r / min. The mixture was then placed in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine was 220°C, and the injection pressure was 65 MPa to obtain a wear-resistant and aging-resistant 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, and the temperature was controlled at 40°C under nitrogen protection. The mixture was stirred and dispersed uniformly. 0.43 mol of triethylamine was added thereto and 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 warm for 4 hours at room temperature. After the reaction was completed, the mixture was filtered, washed with ethyl acetate, and dried to obtain intermediate product B.

[0042] (3) 50 mmol of intermediate product B, 1000 mmol of SnCl2, and 200 mL of concentrated hydrochloric acid were added to an ethanol solvent, heated to 85°C under magnetic stirring, and reacted for 6 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with acetone, and then dissolved in deionized water, filtered, and the pH was adjusted to 9 using 1 mol / L sodium hydroxide solution. The mixture was filtered and dried to obtain intermediate product C.

[0043] (4) At 0°C and under nitrogen protection, 10 mmol of the intermediate product C was added to an acetonitrile solvent and stirred to mix evenly. 40 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added thereto, and then 0.2 mol / L of triethylamine acetonitrile solution was added thereto. The pH of the reaction system was controlled to be 10, and the mixture was stirred for 1 hour. The mixture was heated to 55°C and reacted for 24 hours. After the reaction was completed, the mixture was distilled under reduced pressure, and dichloromethane was added thereto. The mixture was washed with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution in sequence. The mixture was distilled under reduced pressure, washed with deionized water, and dried to obtain a biphenyl phosphate-based hindered phenol antioxidant component.

[0044] (5) 6 mmol of intermediate product C was added to ethanol solvent and magnetically stirred for 40 min. Then 1 g of graphene oxide was added thereto. The temperature was controlled at 90 °C and the reaction was stirred at constant temperature for 34 h. After the reaction was completed, deionized water and ethanol were used for washing in sequence. The product was then dissolved in deionized water, ultrasonically treated for 3 h, filtered, and dried to obtain modified graphene.

[0045] (6) 100 g of PP powder, 0.7 g of biphenyl phosphate-based hindered phenol antioxidant component, and 4 g of modified graphene were added to a high-speed mixer and mixed evenly. The mixture was then placed in a twin-screw extruder for extrusion granulation. The temperatures of each section of the twin-screw extruder were 180°C, 190°C, 200°C, and 190°C, and the screw speed was 120 r / min. The mixture was then placed in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine was 220°C, and the injection pressure was 65 MPa to obtain a wear-resistant and aging-resistant 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, and the temperature was controlled at 40°C under nitrogen protection. The mixture was stirred and dispersed uniformly. 0.44 mol of triethylamine was added thereto and 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.

[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 warm for 2 h at room temperature. After the reaction was completed, the mixture was filtered, washed with ethyl acetate, and dried to obtain intermediate product B.

[0049] (3) 50 mmol of intermediate product B, 1000 mmol of SnCl2, and 200 mL of concentrated hydrochloric acid were added to an ethanol solvent, heated to 80°C under magnetic stirring, and reacted for 6 h. After the reaction was completed, it was cooled to room temperature, filtered, washed with acetone, and then dissolved in deionized water, filtered, and the pH was adjusted to 10 using 1 mol / L sodium hydroxide solution. It was filtered and dried to obtain intermediate product C.

[0050] (4) At 0°C and under nitrogen protection, 10 mmol of the intermediate product C was added to an acetonitrile solvent and stirred to mix evenly. 45 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added thereto, and then 0.2 mol / L of triethylamine acetonitrile solution was added thereto. The pH of the reaction system was controlled to be 10, and the mixture was stirred for 1 hour. The mixture was heated to 55°C and reacted for 26 hours. After the reaction was completed, the mixture was distilled under reduced pressure, and dichloromethane was added thereto. The mixture was washed with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution in sequence. The mixture was distilled under reduced pressure, washed with deionized water, and dried to obtain a biphenyl phosphate-based hindered phenol 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 thereto. The temperature was controlled at 90 °C and the reaction was stirred at constant temperature for 34 h. After the reaction was completed, deionized water and ethanol were used for washing in sequence. The product was then dissolved in deionized water, ultrasonically treated for 2 h, filtered, and dried to obtain modified graphene.

[0052] (6) 100 g of PP powder, 0.8 g of biphenyl phosphate-based hindered phenol antioxidant component, and 5 g of modified graphene were added to a high-speed mixer and mixed evenly. The mixture was then placed in a twin-screw extruder for extrusion granulation. The temperatures of each section of the twin-screw extruder were 180°C, 190°C, 200°C, and 190°C, and the screw speed was 120 r / min. The mixture was then placed in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine was 220°C, and the injection pressure was 65 MPa to obtain a wear-resistant and aging-resistant 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, and the temperature was controlled at 40°C under nitrogen protection. The mixture was stirred and dispersed uniformly. 0.43 mol of triethylamine was added thereto and 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.

[0055] (2) Add 80 mmol of intermediate product A, 176 mmol of 3,5-dinitroaniline, and 100 mmol of triethylamine to dichloromethane solvent, stir and disperse, and keep warm at room temperature for 3 hours. After the reaction is completed, filter, wash with ethyl acetate, and dry to obtain intermediate product B.

[0056] (3) 50 mmol of intermediate product B, 900 mmol of SnCl2, and 200 mL of concentrated hydrochloric acid were added to an ethanol solvent, heated to 85°C under magnetic stirring, and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with acetone, and then dissolved in deionized water. The mixture was filtered and the pH was adjusted to 9 using a 1 mol / L sodium hydroxide solution. The mixture was filtered and dried to obtain an intermediate product C.

[0057] (4) At 0°C and under nitrogen protection, 10 mmol of the intermediate product C was added to an acetonitrile solvent and stirred to mix evenly. 40 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was added thereto, and then 0.2 mol / L of triethylamine acetonitrile solution was added thereto. The pH of the reaction system was controlled to be 10, and the mixture was stirred for 2 h. The mixture was heated to 55°C and reacted for 24 h. After the reaction was completed, the mixture was distilled under reduced pressure, and dichloromethane was added thereto. The mixture was washed with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution in sequence. The mixture was distilled under reduced pressure, washed with deionized water, and dried to obtain a biphenyl phosphate-based hindered phenol antioxidant component.

[0058] (5) 8 mmol of the intermediate product C was added to an ethanol solvent and magnetically stirred for 30 min. Then, 1 g of graphene oxide was added thereto. The temperature was controlled at 85 °C and the reaction was stirred at constant temperature for 34 h. After the reaction was completed, deionized water and ethanol were used for washing in sequence. The product was then dissolved in deionized water, ultrasonically treated for 3 h, filtered, and dried to obtain modified graphene.

[0059] (6) 100 g of PP powder, 1 g of biphenyl phosphate-based hindered phenol antioxidant component, and 6 g of modified graphene were added to a high-speed mixer and mixed evenly. The mixture was then placed in a twin-screw extruder for extrusion granulation. The temperatures of each section of the twin-screw extruder were 180°C, 190°C, 200°C, and 190°C, and the screw speed was 120 r / min. The mixture was then placed in an injection molding machine for injection molding. The nozzle temperature of the injection molding machine was 220°C, and the injection pressure was 65 MPa to obtain a wear-resistant and aging-resistant PP material.

[0060] Comparative Example 1

[0061] The difference between this comparative example and Example 1 is that step (6) does not contain a biphenyl phosphate-based 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 sample was subjected to UV accelerated aging test according to ASTM G154 Cycle 1, with a radiation wavelength of 340nm and an ultraviolet radiation intensity of 0.98W / m 2 , continuous lighting is used and the blackboard temperature is 50℃.

[0065] With reference 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 the present invention exhibits excellent mechanical properties and aging resistance. 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 degradation of the PP chain and reducing the tensile strength of the PP. The biphenyl phosphate-based hindered phenol antioxidant component prepared by the present invention contains a hindered phenol structure that can capture free radicals, reducing free radical degradation of the PP material and improving the mechanical properties after aging.

[0070] Use a limiting oxygen index meter to test the limiting oxygen index of the material.

[0071] The friction and wear test was carried out using a friction and wear testing machine at room temperature and pressure, with a load of 200 N and an experimental time of 1 h.

[0072] Table 2:

[0073]

[0074]

[0075] It can be seen from the table that the PP material prepared by the present 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, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various 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. Add the intermediate product C to an ethanol solvent, stir magnetically for 30-40 minutes, then add graphene oxide thereto, control the temperature to 85-90°C, and stir at constant temperature for 32-36 hours. After the reaction is completed, wash with deionized water and ethanol in sequence, then dissolve the product in deionized water, ultrasonically treat for 2-3 hours, filter, and dry to obtain modified graphene, wherein the structural formula of the intermediate product C is: S2. At 0°C and under nitrogen protection, the intermediate product C is added to an acetonitrile solvent, stirred and mixed uniformly, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is added thereto, and then a 0.2 mol / L triethylamine acetonitrile solution is added thereto, the pH of the reaction system is controlled to be 9-10, stirred for 1-2 hours, heated to 50-60°C, and reacted for 22-26 hours. After the reaction is completed, distilled under reduced pressure, dichloromethane is added thereto, and washed with 5% NaHCO3 solution, 0.5 mol / L hydrochloric acid solution, and saturated NaCl solution in sequence, distilled under reduced pressure, washed with deionized water, and dried to obtain a biphenyl phosphate-based hindered phenol antioxidant component; S3. Add PP powder, biphenyl phosphate-based hindered phenol antioxidant component, and modified graphene into a high-speed mixer, mix them evenly, place them in a twin-screw extruder, extrude them into granules, and then place them in an injection molding machine for injection molding to obtain wear-resistant and aging-resistant PP material.

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

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

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

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

6. The wear-resistant and aging-resistant 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'-tetrahydroxybiphenyl were added to a dichloromethane solvent, and under nitrogen protection, the temperature was controlled at 35-40°C, and the mixture was stirred and dispersed uniformly. Triethylamine was added thereto, and the mixture was reacted 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 an intermediate product A; (2) Add intermediate product A, 3,5-dinitroaniline, and triethylamine to dichloromethane solvent, stir and disperse, and keep warm for 2-4 hours at room temperature. After the reaction is completed, filter, wash with ethyl acetate, and dry to obtain intermediate product B; (3) Add the intermediate product B, SnCl2, and concentrated hydrochloric acid to an ethanol solvent, raise the temperature to 80-85°C under magnetic stirring, and react for 4-6 hours. After the reaction is completed, cool to room temperature, filter, wash with acetone, and then dissolve in deionized water, filter, and adjust the pH to 9-10 with 1 mol / L sodium hydroxide solution. Filter and dry to obtain the intermediate product C.

7. The wear-resistant and aging-resistant PP material according to claim 6, characterized in that: In the above-mentioned (1), the usage ratio of phosphorus oxychloride, 2,2',6,6'-tetrahydroxybiphenyl and triethylamine is (2-2.2) mol:1 mol:(4.2-4.4) mol.

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

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

10. Use of the wear-resistant and aging-resistant PP material according to claim 1 in daily plastic products.

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