An anti-aging enhanced PP daily-use plastic product and its preparation method

Abstract

The present invention relates to the technical field of polymer materials, and discloses an anti-aging enhanced PP daily-use plastic product and a preparation method thereof. The anti-aging enhanced PP daily-use plastic product comprises the following raw materials in parts by weight: The anti-aging enhanced PP daily-use plastic product comprises the following raw materials in parts by weight: 80-95 parts of polypropylene, 20-30 parts of functionalized polypropylene, 1.5-3 parts of a composite flame retardant, 5-8 parts of modified nanoparticles, 8-15 parts of a toughening agent, and 0.5-2 parts of a lubricant. The functionalized polypropylene is obtained by copolymerizing a long-chain α-olefin monomer containing a diphenylamine group with a propylene monomer. The modified nanoparticles are titanium dioxide-nano zinc oxide hybrid nanoparticles grafted with a cyclotriphosphazene derivative. By adding the functionalized polypropylene and the modified nanoparticles, the anti-aging performance of the material is greatly improved in the present invention.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to an anti-aging enhanced PP daily plastic product and a preparation method thereof. Background Art

[0002] Polypropylene is a high molecular compound obtained by homopolymerization or copolymerization reaction of propylene as the main monomer, ethylene or 1-butene as the comonomer under the action of catalytic systems such as Ziegler-Natta catalysts or metallocene catalysts. Due to its good mechanical properties, light texture, chemical corrosion resistance and easy processing and molding, it is widely used in daily necessities, household appliances and other fields.

[0003] However, the molecular chain structure of polypropylene is single, and under the influence of ultraviolet rays, heat and oxygen, it is prone to phenomena such as yellowing, sticking, and decline in mechanical properties of the appearance. At present, ultraviolet absorbers and light stabilizers are usually added to polypropylene materials to improve their anti-aging performance. However, these small molecule anti-aging agents are prone to migration and precipitation, resulting in a decline in the anti-aging performance of polypropylene plastics. Summary of the Invention

[0004] To solve the deficiencies mentioned in the above background art, the purpose of the present invention is to provide an anti-aging enhanced PP daily plastic product and a preparation method thereof. By adding functionalized polypropylene and modified nanoparticles, the anti-aging performance of the material is greatly improved.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] An anti-aging enhanced PP daily plastic product, the anti-aging enhanced PP daily plastic product comprises the following raw materials in parts by weight: 80-95 parts of polypropylene, 20-30 parts of functionalized polypropylene, 1.5-3 parts of composite flame retardant, 5-8 parts of modified nanoparticles, 8-15 parts of toughening agent, 0.5-2 parts of lubricant;

[0007] The functionalized polypropylene is obtained by copolymerizing a long-chain α-olefin monomer containing a diphenylamine group with a propylene monomer;

[0008] The modified nanoparticles are titanium dioxide-nano zinc oxide hybrid nanoparticles grafted with cyclotriphosphazene derivatives, and the cyclotriphosphazene derivatives contain a hindered amine structure and a siloxane structure.

[0009] Further preferably, the toughening agent is one of ethylene-octene copolymer, ethylene-vinyl acetate copolymer or ethylene propylene diene monomer rubber.

[0010] Further preferably, the lubricant is one or several of stearates, paraffin wax, and polyethylene wax.

[0011] Further preferably, the composite flame retardant is prepared by mixing aluminum hydroxide, ammonium polyphosphate, pentaerythritol, and melamine in a mass ratio of 1:0.5:0.2:0.2.

[0012] Further preferably, the preparation method of the functionalized polypropylene comprises the following steps:

[0013] (1) Under a nitrogen atmosphere, 4-bromophenylaniline and potassium tert-butoxide are added to tetrahydrofuran, stirred and dissolved at -50°C, then a pentane solution of tert-butyllithium is slowly added dropwise. After the addition is complete, the temperature is raised to 0°C, and 8-bromo-1-octene in an equimolar amount to 4-bromophenylaniline is added, and the mixture is stirred and reacted for 8-12 h;

[0014] After the reaction is completed, the reaction solution is quenched with a saturated ammonium chloride solution, the organic phase is extracted with ether, then rotary evaporated, dried with anhydrous magnesium sulfate, filtered to remove impurities, and silica gel column chromatography is carried out using n-hexane as the developing agent. The product is obtained as a long-chain α-olefin monomer after vacuum distillation under reduced pressure;

[0015] (3) Under vacuum conditions, toluene, the long-chain α-olefin monomer, and triisobutylaluminum are added to a high-pressure polymerization kettle. After stirring for 3-5 min, triphenylmethylcarbenium tetrakis(pentafluorophenyl)borate and a metallocene catalyst are added, and high-pressure propylene is introduced. The mixture is stirred and reacted at 50°C for 8-12 min. The obtained polymer is precipitated from an ethanol solution of 2 vol% hydrochloric acid, filtered, washed three times with ethanol, and then dried to a constant weight in a vacuum drying oven to obtain the functionalized polypropylene.

[0016] Further preferably, the molar ratio of the long-chain α-olefin monomer to the propylene monomer is 1:80-100.

[0017] Further preferably, the preparation method of the modified nanoparticles comprises the following steps:

[0018] A. Add nano-titanium dioxide powder to ionized water, ultrasonically disperse for 5-10 min, then add zinc nitrate hexahydrate and sodium dodecylbenzenesulfonate, continue to ultrasonically disperse for 40-60 min, add a 3 wt% urea solution, and heat in an 80°C environment for 1-3 h. The product is filtered, washed, and then calcined in a tube furnace at 350°C for 3-5 h to obtain hybrid nanoparticles;

[0019] B. Add hexachlorocyclotriphosphazene to tetrahydrofuran and triethylamine under a nitrogen atmosphere, stir to dissolve hexachlorocyclotriphosphazene, then slowly dropwise add 3-aminopropyltriethoxysilane at a uniform speed. After the addition is completed, react in an ice bath for 1 - 3 h. Then add 2,2,6,6-tetramethylpiperidineamine to the reaction system, gradually heat to 60 °C, and keep the temperature for reaction for 5 - 10 h. After the reaction is completed, cool and filter to remove triethylamine hydrochloride, distill off tetrahydrofuran under reduced pressure, wash with deionized water 3 - 5 times, add ethyl acetate to the separated organic phase, dry and then filter. The filtrate is distilled under reduced pressure to obtain a cyclotriphosphazene derivative;

[0020] C. Add the hybrid nanoparticles to an ethanol aqueous solution of 95 vol% according to a solid-liquid ratio of 1:5 - 8, ultrasonically disperse for 10 - 15 min, adjust the pH of the solution to 4 with an aqueous hydrochloric acid solution, then slowly add the cyclotriphosphazene derivative to the hybrid nanoparticle dispersion, continue to ultrasonically disperse for 5 - 10 min, heat to 60 - 80 °C and keep the temperature for reaction for 3 - 5 h. After cooling, filter, wash, and dry to obtain modified nanoparticles.

[0021] Further preferably, the mass ratio of titanium dioxide nanoparticles, zinc nitrate hexahydrate, and sodium dodecylbenzenesulfonate is 1:5 - 6:3.

[0022] Further preferably, the molar ratio of hexachlorocyclotriphosphazene, 3-aminopropyltriethoxysilane, and 2,2,6,6-tetramethylpiperidineamine is 1:1:5.

[0023] A preparation method of an anti-aging enhanced PP daily plastic product, comprising the following steps:

[0024] S1. Add polypropylene, functionalized polypropylene, toughening agent, and lubricant to a high-speed mixer and mix well for 10 - 20 min. Then melt, plasticize, and blend the mixture through a twin-screw extruder, and extrude and pelletize to obtain polymer pellets;

[0025] S2. Premix the polymer pellets with the modified nanoparticles and the composite flame retardant in a high-speed mixer, then melt and blend the mixture through a twin-screw extruder, extrude and pelletize, and dry to obtain anti-aging enhanced polypropylene pellets;

[0026] S3. Put the anti-aging enhanced polypropylene pellets into an injection molding machine to heat and melt. The high-temperature molten anti-aging enhanced polypropylene is injected into a daily plastic product mold under high pressure. Wait for the plastic in the mold to cool and solidify to form an anti-aging enhanced PP daily plastic product.

[0027] The beneficial effects of the present invention:

[0028] The anti-aging enhanced PP daily-use products of the present invention greatly improve the anti-aging performance of the material by adding functionalized polypropylene and modified nanoparticles. Among them, the functionalized polypropylene of the present invention is obtained by copolymerizing propylene monomers with long-chain α-olefin monomers containing diphenylamine groups, introducing diphenylamine groups into the polymer chain, and obtaining a polypropylene material with diphenylamine groups on the side chain, thereby enhancing its anti-aging performance. The modified nanoparticles of the present invention are prepared by ultrasonic microwave homogeneous precipitation method to prepare nano-Ti 2 -ZnO hybrid materials, covering ZnO on the surface of nano-Ti 2 , covering its superoxide radical active sites, and then grafting cyclotriphosphazene derivatives on the surface, which can improve the dispersibility of the hybrid nanoparticles in the polymer, and the cyclotriphosphazene derivatives contain abundant hindered amine groups, which together with TiO 2 play an anti-ultraviolet oxidation role. Specific embodiments

[0029] 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 a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the protection scope of the present invention.

[0030] Example 1

[0031] A kind of functionalized polypropylene is obtained by copolymerizing long-chain α-olefin monomers containing diphenylamine groups with propylene monomers. The preparation method includes the following steps:

[0032] (1) Under a nitrogen atmosphere, 4.9 g of 4-bromophenylaniline and 0.27 g of potassium tert-butoxide are added to 60 ml of tetrahydrofuran, stirred and dissolved at -50 °C, then 40 ml of a pentane solution of tert-butyllithium is slowly added dropwise. After the addition is completed, the temperature is raised to 0 °C, and 8.1 g of 8-bromo-1-octene is added, and the reaction is stirred for 10 h;

[0033] (2) After the reaction is completed, the reaction solution is quenched with saturated ammonium chloride solution, extracted with ether, the organic phase is rotary evaporated, then dried with anhydrous magnesium sulfate, filtered to remove impurities, and finally n-hexane is used as the eluent for silica gel column chromatography. The product is obtained by vacuum distillation under reduced pressure to obtain long-chain α-olefin monomers;

[0034] (3) Under vacuum conditions, 200 ml of toluene, 1.2 g of long-chain α-olefin monomer, and 0.3 g of triisobutylaluminum were added to a high-pressure polymerization kettle. After stirring for 4 min, 0.03 g of triphenylmethyl carbonium tetrakis(pentafluorophenyl)borate and 0.1 g of metallocene catalyst were added. Then, 42 g of high-pressure propylene was introduced, and the mixture was stirred and reacted at 50 °C for 10 min. The resulting polymer was precipitated from an ethanol solution of 2 vol% hydrochloric acid, filtered, washed three times with ethanol, and then dried to a constant weight in a vacuum drying oven to obtain functionalized polypropylene.

[0035] Example 2

[0036] A modified nanoparticle, which is a titanium dioxide-nanozinc oxide hybrid nanoparticle grafted with a cyclotriphosphazene derivative. The cyclotriphosphazene derivative contains a hindered amine structure and a siloxane structure. The preparation method of the above modified nanoparticle includes the following steps:

[0037] A. Add 2.1 g of nano-titanium dioxide powder to 100 ml of ionized water, ultrasonically disperse for 8 min, then add 11.5 g of zinc nitrate hexahydrate and 6.3 g of sodium dodecylbenzenesulfonate, continue ultrasonically disperse for 50 min, add 20 ml of 3 wt% urea solution, and heat in an 80 °C environment for 2 h. After the product is filtered and washed, it is calcined in a 350 °C tube furnace for 4 h to obtain hybrid nanoparticles;

[0038] B. Under a nitrogen atmosphere, add 6.9 g of hexachlorocyclotriphosphazene to 50 ml of tetrahydrofuran and 20 ml of triethylamine, stir to dissolve the hexachlorocyclotriphosphazene, then slowly dropwise add 4.4 g of 3-aminopropyltriethoxysilane. After the addition is completed, react in an ice bath for 2 h. Then add 15.6 g of 2,2,6,6-tetramethylpiperidineamine to the reaction system, gradually heat to 60 °C, and keep the temperature for 8 h. After the reaction is completed, cool, filter to remove triethylamine hydrochloride, distill off tetrahydrofuran under reduced pressure, wash 3 - 5 times with deionized water, add ethyl acetate to the separated organic phase, dry and then filter. The filtrate is distilled under reduced pressure to obtain the cyclotriphosphazene derivative;

[0039] C. Add the hybrid nanoparticles to a 95 vol% ethanol aqueous solution according to a solid-liquid ratio of 1:6, ultrasonically disperse for 12 min, adjust the pH of the solution to 4 with an aqueous hydrochloric acid solution, then slowly add the cyclotriphosphazene derivative to the hybrid nanoparticle dispersion, continue ultrasonically disperse for 8 min, heat to 70 °C and keep the temperature for 4 h. After cooling, filter, wash, and dry to obtain the modified nanoparticles.

[0040] Example 3

[0041] An anti-aging enhanced PP daily plastic product, which is injection-molded from anti-aging polypropylene material. The anti-aging polypropylene material comprises the following raw materials in parts by weight: 80 parts of polypropylene, 30 parts of functionalized polypropylene, 0.8 part of aluminum hydroxide, 0.4 part of ammonium polyphosphate, 0.16 part of pentaerythritol, 0.16 part of melamine, 8 parts of modified nanoparticles, 8 parts of ethylene-octene copolymer, and 2 parts of polyethylene wax; the functionalized polypropylene is obtained by copolymerizing a long-chain α-olefin monomer containing a diphenylamine group prepared in Example 1 with a propylene monomer; the modified nanoparticles are titanium dioxide-nano zinc oxide hybrid nanoparticles grafted with cyclotriphosphazene derivatives prepared in Example 2.

[0042] The preparation method of the above anti-aging enhanced PP daily plastic product comprises the following steps:

[0043] S1. Add polypropylene, functionalized polypropylene, ethylene-octene copolymer, and polyethylene wax into a high-speed mixer and mix well for 10 min. Then, melt, plasticize, and blend the mixture through a twin-screw extruder, and extrude and pelletize to obtain polymer pellets;

[0044] S2. Add the polymer pellets, modified nanoparticles, aluminum hydroxide, ammonium polyphosphate, pentaerythritol, and melamine into a high-speed mixer for premixing. Then, melt and blend the mixture through a twin-screw extruder, extrude and pelletize, and dry to obtain the anti-aging polypropylene material;

[0045] S3. Put the anti-aging polypropylene material into an injection molding machine to heat and melt it. The high-temperature molten anti-aging enhanced polypropylene is injected into the daily plastic product mold under high pressure. Wait for the plastic in the mold to cool and solidify to form the anti-aging enhanced PP daily plastic product.

[0046] Example 4

[0047] An anti-aging enhanced PP daily plastic product, which is injection-molded from anti-aging polypropylene material. The anti-aging polypropylene material comprises the following raw materials in parts by weight: 95 parts of polypropylene, 20 parts of functionalized polypropylene, 1.6 parts of aluminum hydroxide, 0.8 part of ammonium polyphosphate, 0.32 part of pentaerythritol, 0.32 part of melamine, 5 parts of modified nanoparticles, 15 parts of ethylene-vinyl acetate copolymer, and 0.5 part of paraffin; the functionalized polypropylene is obtained by copolymerizing a long-chain α-olefin monomer containing a diphenylamine group prepared in Example 1 with a propylene monomer; the modified nanoparticles are titanium dioxide-nano zinc oxide hybrid nanoparticles grafted with cyclotriphosphazene derivatives prepared in Example 2.

[0048] The preparation method of the above anti-aging enhanced PP daily plastic product comprises the following steps:

[0049] S1. Add polypropylene, functionalized polypropylene, ethylene-vinyl acetate copolymer, and paraffin into a high-speed mixer and mix well for 20 min. Then, melt, plasticize, and blend the mixture through a twin-screw extruder, and extrude and pelletize to obtain polymer pellets.

[0050] S2. Premix the polymer pellets with modified nanoparticles, aluminum hydroxide, ammonium polyphosphate, pentaerythritol, and melamine in a high-speed mixer. Then, melt and blend the mixture through a twin-screw extruder, extrude and pelletize, and dry to obtain the anti-aging polypropylene material.

[0051] S3. Put the anti-aging polypropylene material into an injection molding machine to heat and melt it. Inject the high-temperature molten anti-aging reinforced polypropylene into the daily plastic product mold under high pressure. Wait for the plastic in the mold to cool and solidify to form the anti-aging reinforced PP daily plastic product.

[0052] Example 5

[0053] An anti-aging reinforced PP daily plastic product is injection-molded from the anti-aging polypropylene material. The anti-aging polypropylene material comprises the following raw materials in parts by weight: 88 parts of polypropylene, 25 parts of functionalized polypropylene, 1.2 parts of aluminum hydroxide, 0.6 part of ammonium polyphosphate, 0.24 part of pentaerythritol, 0.24 part of melamine, 6 parts of modified nanoparticles, 12 parts of ethylene propylene diene monomer rubber, and 1.2 parts of sodium stearate. The functionalized polypropylene is obtained by copolymerizing a long-chain α-olefin monomer containing a diphenylamine group and a propylene monomer prepared in Example 1. The modified nanoparticles are titanium dioxide-nano zinc oxide hybrid nanoparticles grafted with cyclotriphosphazene derivatives prepared in Example 2.

[0054] The preparation method of the above anti-aging reinforced PP daily plastic product comprises the following steps:

[0055] S1. Add polypropylene, functionalized polypropylene, ethylene propylene diene monomer rubber, and sodium stearate into a high-speed mixer and mix well for 15 min. Then, melt, plasticize, and blend the mixture through a twin-screw extruder, and extrude and pelletize to obtain polymer pellets.

[0056] S2. Premix the polymer pellets with modified nanoparticles, aluminum hydroxide, ammonium polyphosphate, pentaerythritol, and melamine in a high-speed mixer. Then, melt and blend the mixture through a twin-screw extruder, extrude and pelletize, and dry to obtain the anti-aging polypropylene material.

[0057] S3. Put the anti-aging polypropylene material into an injection molding machine to heat and melt it. Inject the high-temperature molten anti-aging reinforced polypropylene into the daily plastic product mold under high pressure. Wait for the plastic in the mold to cool and solidify to form the anti-aging reinforced PP daily plastic product.

[0058] Comparative Example 1

[0059] An anti-aging enhanced PP daily plastic product is injection-molded from an anti-aging polypropylene material. The anti-aging polypropylene material comprises the following raw materials in parts by weight: 88 parts of polypropylene, 1.2 parts of aluminum hydroxide, 0.6 part of ammonium polyphosphate, 0.24 part of pentaerythritol, 0.24 part of melamine, 6 parts of modified nanoparticles, 12 parts of ethylene propylene diene monomer (EPDM), and 1.2 parts of sodium stearate; the modified nanoparticles are titanium dioxide-nano zinc oxide hybrid nanoparticles grafted with cyclotriphosphazene derivatives prepared in Example 2.

[0060] The preparation method of the above anti-aging enhanced PP daily plastic product comprises the following steps:

[0061] S1. Add polypropylene, EPDM, and sodium stearate into a high-speed mixer and mix well for 15 min. Then, melt, plasticize, and blend the mixture through a twin-screw extruder, and extrude and pelletize to obtain polymer pellets.

[0062] S2. Add the polymer pellets, modified nanoparticles, aluminum hydroxide, ammonium polyphosphate, pentaerythritol, and melamine into a high-speed mixer for premixing. Then, melt and blend the mixture through a twin-screw extruder, extrude and pelletize, and dry to obtain the anti-aging polypropylene material.

[0063] S3. Put the anti-aging polypropylene material into an injection molding machine to heat and melt it. Inject the high-temperature molten anti-aging enhanced polypropylene into the mold of the daily plastic product under high pressure. Wait for the plastic in the mold to cool and solidify to form the anti-aging enhanced PP daily plastic product.

[0064] Comparative Example 2

[0065] An anti-aging enhanced PP daily plastic product is injection-molded from an anti-aging polypropylene material. The anti-aging polypropylene material comprises the following raw materials in parts by weight: 88 parts of polypropylene, 25 parts of functionalized polypropylene, 1.2 parts of aluminum hydroxide, 0.6 part of ammonium polyphosphate, 0.24 part of pentaerythritol, 0.24 part of melamine, 12 parts of EPDM, and 1.2 parts of sodium stearate; the functionalized polypropylene is obtained by copolymerizing a long-chain α-olefin monomer containing a diphenylamine group and a propylene monomer prepared in Example 1.

[0066] The preparation method of the above anti-aging enhanced PP daily plastic product comprises the following steps:

[0067] S1. Add polypropylene, functionalized polypropylene, EPDM, and sodium stearate into a high-speed mixer and mix well for 15 min. Then, melt, plasticize, and blend the mixture through a twin-screw extruder, and extrude and pelletize to obtain polymer pellets.

[0068] S2. Add the polymer pellets, aluminum hydroxide, ammonium polyphosphate, pentaerythritol, and melamine into a high-speed mixer for premixing. Then, melt and blend the mixture through a twin-screw extruder, extrude and pelletize, and dry to obtain the anti-aging polypropylene material.

[0069] S3. Put the anti-aging polypropylene material into an injection molding machine to heat and melt it. The high-temperature molten anti-aging reinforced polypropylene is injected into the daily plastic product mold under high pressure. Wait for the plastic in the mold to cool and solidify to form an anti-aging reinforced PP daily plastic product.

[0070] Performance testing

[0071] I. Light stability test

[0072] Cut the anti-aging reinforced PP daily plastic products prepared in Examples 3 - 5 and Comparative Examples 1 - 2 into specimens of 30 mm×30 mm, put them into an ultraviolet lamp box for accelerated aging, and conduct light stability performance testing. Take samples every 10 h to test their tensile strength. The tensile strength test refers to GB / T 528 - 2009. Cut the molded specimens into dumbbell-shaped tensile splines of 25 mm×4 mm, with a tensile rate of 20 mm / min. Compare with the initial tensile strength to calculate the tensile strength retention rate. The data obtained are shown in Table 1 below.

[0073] Table 1 Test results of light stability performance of anti-aging reinforced PP daily plastic products

[0074]

[0075] It can be seen from the data in Table 1 that the decline in the tensile strength of the anti-aging reinforced PP daily plastic product in Comparative Example 2 after ultraviolet accelerated aging is larger than that of other groups, indicating that the light stability of the material without adding modified nanoparticles is worse than that of other groups. In this invention, the modified nanoparticles are prepared by ultrasonic microwave homogeneous precipitation method to prepare nano-TiO 2 -ZnO hybrid material. Cover ZnO on the surface of nano-TiO 2 to cover its superoxide free radical active sites, and then graft cyclotriphosphazene derivatives on the surface, which can improve the dispersion of the hybrid nanoparticles in the polymer. And the cyclotriphosphazene derivatives contain rich hindered amine groups, which play an anti-ultraviolet oxidation role together with TiO 2

[0076] II. Thermal stability performance test

[0077] After aging the anti-aging reinforced PP daily plastic products prepared in Examples 3 - 5 and Comparative Examples 1 - 2 at 100 °C for 24 h, 48 h, and 72 h respectively, test their tensile strength. The tensile strength test refers to GB / T 528 - 2009. Cut the molded specimens into dumbbell-shaped tensile splines of 25 mm×4 mm, with a tensile rate of 20 mm / min. Compare with the initial tensile strength to calculate the tensile strength retention rate. The data obtained are shown in Table 2.

[0078] ​Table 2 Test Results of Thermal Stability Performance of Anti-aging Enhanced PP Daily-use Plastics

[0079]

[0080] As can be seen from the data in Table 2, the decline in the tensile strength of the anti-aging enhanced PP daily-use plastics in Comparative Example 1 after thermal aging is larger than that of other groups, indicating that the light stability of the material without functionalized polypropylene is worse than that of other groups. The functionalized polypropylene of the present invention is obtained by copolymerizing propylene monomer with a long-chain α-olefin monomer containing a diphenylamine group, introducing the diphenylamine group into the polymer chain, thereby improving its anti-aging performance.

[0081] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0082] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification only illustrates the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. An anti-aging reinforced PP Japanese plastic product, characterized in that: The anti-aging enhanced PP Japanese plastic product is injection molded by anti-aging polypropylene material, and the anti-aging polypropylene material includes the following raw materials by weight: 80-95 parts of polypropylene, 20-30 parts of functionalized polypropylene, 1.5-3 parts of composite flame retardant, 5-8 parts of modified nanoparticles, 8-15 parts of toughening agent, and 0.5-2 parts of lubricant; The functionalized polypropylene is obtained by copolymerizing a long-chain α-olefin monomer containing a diphenylamine group and a propylene monomer; The modified nanoparticles are titanium dioxide-nano zinc oxide hybrid nanoparticles grafted with cyclotriphosphazene derivatives, wherein the cyclotriphosphazene derivatives contain hindered amine structures and siloxane structures. The preparation method of the modified nanoparticles comprises the following steps: A. Add nano titanium dioxide powder to ionized water, ultrasonically disperse for 5-10 minutes, then add zinc nitrate hexahydrate and sodium dodecylbenzene sulfonate, continue ultrasonically dispersing for 40-60 minutes, add 3wt% urea solution, and heat at 80°C for 1-3 hours. After filtering and washing the product, place it in a 350°C tubular furnace and calcine it for 3-5 hours to obtain hybrid nanoparticles; B. Add hexachlorocyclotriphosphazene to tetrahydrofuran and triethylamine under nitrogen atmosphere, stir to dissolve the hexachlorocyclotriphosphazene, then uniformly add 3-aminopropyltriethoxysilane, react in an ice bath for 1-3 hours after the addition is complete, then add 2,2,6,6-tetramethylpiperidinamine to the reaction system, heat to 60°C in a gradient manner, and keep the temperature for 5-10 hours. After the reaction is complete, cool and filter to remove triethylamine hydrochloride, remove tetrahydrofuran by vacuum distillation, wash with deionized water for 3-5 times, add ethyl acetate to the separated organic phase, dry and filter, and vacuum distill the filtrate to obtain a cyclotriphosphazene derivative; C. Add the hybrid nanoparticles into a 95 vol% ethanol aqueous solution at a solid-liquid ratio of 1:5-8, ultrasonically disperse for 10-15 min, adjust the pH of the solution to 4 with a hydrochloric acid aqueous solution, then slowly add the cyclotriphosphazene derivative into the hybrid nanoparticle dispersion, continue ultrasonically dispersing for 5-10 min, heat to 60-80°C and keep the reaction for 3-5 h, filter after cooling, wash, and dry to obtain the modified nanoparticles.

2. The anti-aging reinforced PP Japanese plastic product according to claim 1, characterized in that: The toughening agent is one of ethylene-octene copolymer, ethylene-vinyl acetate copolymer or ethylene propylene diene monomer rubber.

3. The anti-aging reinforced PP plastic product according to claim 1, characterized in that: The lubricant is one or more of stearate, paraffin and polyethylene wax.

4. The anti-aging reinforced PP plastic product according to claim 1, characterized in that: The composite flame retardant is prepared by mixing aluminum hydroxide, ammonium polyphosphate, pentaerythritol and melamine in a mass ratio of 1:0.5:0.2:0.

2.

5. The anti-aging reinforced PP plastic product according to claim 1, characterized in that: The preparation method of the functionalized polypropylene comprises the following steps: (1) Add 4-bromophenylaniline and potassium tert-butoxide to tetrahydrofuran under nitrogen atmosphere, stir and dissolve at -50°C, then slowly dropwise add tert-butyllithium in pentane solution, raise the temperature to 0°C after the addition is complete, add 8-bromo-1-octene in an equal molar amount to 4-bromophenylaniline, and stir to react for 8-12 hours; (2) After the reaction is completed, the reaction solution is quenched with a saturated ammonium chloride solution, the organic phase is extracted with ether and then rotary evaporated, then dried with anhydrous magnesium sulfate, filtered to remove impurities, and finally n-hexane is used as a developing solvent for silica gel column chromatography. The product is subjected to vacuum distillation to obtain a long-chain α-olefin monomer; (3) Toluene, long-chain α-olefin monomers, and triisobutylaluminum are added to a high-pressure polymerization reactor under vacuum conditions. After stirring for 3 to 5 minutes, tritylcarbonium tetrakis(pentafluorophenyl)borate and a metallocene catalyst are added, and high-pressure propylene is introduced. The reaction is stirred at 50°C for 8 to 12 minutes. The obtained polymer is precipitated from a 2 vol% hydrochloric acid ethanol solution, filtered, washed three times with ethanol, and then dried in a vacuum drying oven to constant weight to obtain functionalized polypropylene.

6. The anti-aging reinforced PP plastic product according to claim 5, characterized in that: The molar ratio of the long-chain α-olefin monomer to the propylene monomer is 1:80-100.

7. The anti-aging reinforced PP plastic product according to claim 1, characterized in that: The mass ratio of the nano titanium dioxide, zinc nitrate hexahydrate and sodium dodecylbenzene sulfonate is 1:5-6:

3.

8. The anti-aging reinforced PP plastic product according to claim 1, characterized in that: The molar ratio of the hexachlorocyclotriphosphazene, 3-aminopropyltriethoxysilane and 2,2,6,6-tetramethylpiperidinamine is 1:1:

5.

9. The method for preparing the anti-aging reinforced PP plastic product according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Add polypropylene, functionalized polypropylene, toughening agent and lubricant into a high mixing pot and mix them thoroughly for 10-20 minutes. Then, melt, plasticize and blend the mixture through a twin-screw extruder, and extrude and granulate to obtain polymer particles. S2, adding polymer particles, modified nanoparticles and composite flame retardant into a high mixing pot for premixing, then melting and blending the mixture through a twin-screw extruder, extruding and granulating, and drying to obtain an anti-aging polypropylene material; S3. Put the anti-aging polypropylene material into the injection molding machine and heat it to melt. The high-temperature molten anti-aging reinforced polypropylene is injected into the plastic product mold under high pressure. The plastic in the mold is cooled and solidified to form an anti-aging reinforced PP plastic product.

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