Rare earth modified high polymer material and preparation method thereof

Abstract

The invention discloses a rare earth modified high polymer material and a preparation method thereof, and relates to the technical field of high polymer materials. When the rare earth modified high polymer material is prepared, nano cerium dioxide and 2-chloroethyltriethoxysilane react to prepare pre-modified nano cerium dioxide; carrying out quaternization reaction on the pre-modified nano cerium dioxide and 7-(diethylamino) coumarin to generate modified nano cerium dioxide; the preparation method comprises the following steps: carrying out melt grafting on pre-irradiated polyethylene, vinyl phosphonic acid and 2-(allyloxy)-4, 6-dichloro-1, 3, 5-triazine to prepare pre-modified polyethylene; the pre-modified polyethylene and N-butyl-2, 2, 6, 6-tetramethyl-4-piperidylamine are subjected to a reaction, and modified polyethylene is prepared; and carrying out melt blending on the modified polyethylene and the modified nano cerium dioxide to prepare the rare earth modified high polymer material. The rare earth modified high polymer material prepared by the invention has good flame retardant property, antibacterial property, tensile strength and anti-aging property.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a rare earth modified polymer material and a preparation method thereof. Background Art

[0002] Rare earth elements (REEs) are a collective term for 17 chemical elements in Group IIIB of the periodic table, including scandium, yttrium, and the lanthanides. Due to their unique 4f electron-level structure, REEs exhibit unique physical and chemical properties, including electrical, magnetic, optical, and catalytic properties. They have significant application value in functional materials and are often referred to as "industrial gold" or "industrial vitamins." Of the 17 REEs, cerium has the highest abundance in the Earth's crust, reaching 68 ppm. Due to its abundance and ease of extraction, cerium is relatively inexpensive compared to other REEs, making it one of the earliest REEs to find practical use.

[0003] Cerium dioxide is a versatile and inexpensive rare earth oxide material with a wide range of applications, including UV absorbers, automotive exhaust catalysts, electronic ceramics, glass coatings, and luminescent materials. Nano-ceria can both absorb and shield UV rays, exhibiting excellent anti-aging properties. Furthermore, ceria's ability to catalyze esterification and dehydrogenation can promote carbonization in polymer matrices, making it a common synergist in flame retardant systems.

[0004] Polyethylene has many excellent properties such as light weight, low price, heat resistance, easy processing, and good chemical corrosion resistance. Therefore, it is widely used in medical equipment, pipelines, chemicals, agriculture, and vehicles and ships. Polyethylene is a long-chain macromolecule composed of two elements, carbon and hydrogen, so it has the disadvantage of being flammable. In addition, polyethylene releases a large amount of heat during the combustion process, accompanied by smoke and dripping, which easily causes the spread of combustion and can cause large-scale fires in a short period of time. At the same time, polyethylene materials are usually used outdoors and are exposed to sunlight all year round, which easily causes the aging of the material. Photoaging can cause polyethylene chain scission and branching, resulting in polyethylene degradation, thereby causing a significant decrease in the mechanical properties of polyethylene, affecting the normal use of the material. Therefore, the present invention prepares a rare earth modified polymer material with good flame retardant properties and anti-aging properties. Summary of the Invention

[0005] The purpose of the present invention is to provide a rare earth modified polymer material and a preparation method thereof, so as to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: A rare earth modified polymer material is prepared by melt blending modified polyethylene and modified nano-cerium dioxide.

[0007] As an optimization, the modified polyethylene is prepared by reacting pre-modified polyethylene with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

[0008] As an optimization, the pre-modified polyethylene is prepared by melt grafting pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine.

[0009] As an optimization, the modified nano-cerium dioxide is prepared by quaternization reaction of pre-modified nano-cerium dioxide and 7-(diethylamino)coumarin.

[0010] As an optimization, the pre-modified nano-cerium dioxide is prepared by reacting nano-cerium dioxide with 2-chloroethyltriethoxysilane.

[0011] A rare earth modified polymer material and a preparation method thereof, comprising the following preparation steps: (1) Pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:(1.2-1.4):(15-20), stirred at 50-60°C and 200-300 r / min for 10-12 h, and N,N-dimethylformamide was removed by rotary evaporation. The obtained product was washed with anhydrous ethanol 2-4 times and vacuum dried at 40-50°C for 10-12 h to obtain modified nano-cerium dioxide; (2) Pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1: (0.1~0.2): (15~20), stirred at 40~60℃, 200~300r / min for 2~4h, 20wt% sodium hydroxide aqueous solution (0.2~0.3 times the mass of pre-modified polyethylene) was added dropwise at a rate of 5ml / min, stirred at 80~100℃, 200~300r / min for 6~8h, cooled to room temperature, filtered, and the filtrate was rotary evaporated to remove N,N-dimethylformamide, deionized water (20~30 times the mass of pre-modified polyethylene) was added, stirred at 300~500r / min for 10~20min at room temperature, filtered, washed with deionized water 2~4 times, and vacuum dried at 60~70℃ for 10~12h to obtain modified polyethylene; (3) The modified polyethylene and modified nano-cerium dioxide are mixed evenly in a mass ratio of 1: (0.04-0.06), added into a twin-screw extruder, melt-extruded, injection-molded, cooled to room temperature, demolded and taken out to obtain a rare earth modified polymer material.

[0012] As an optimization, the preparation process of the pre-modified nano-cerium dioxide in step (1) is as follows: 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution are mixed uniformly in a mass ratio of 1: (10~12), ultrasonically dispersed for 20~40min, nano-cerium dioxide with a mass of 0.1~0.2 times that of 2-chloroethyltriethoxysilane is added, mixed uniformly, ultrasonically dispersed for 30~40min, stirred at 75~80℃ and 200~300r / min for 8~10h, filtered and washed with anhydrous ethanol 2~4 times, and vacuum dried at 60~70℃ for 10~12h to obtain pre-modified nano-cerium dioxide.

[0013] As an optimization, the preparation process of the pre-modified polyethylene in step (2) is as follows: under a nitrogen atmosphere, pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine are uniformly mixed in a mass ratio of 1: (0.02~0.04): (0.04~0.06), added to a torque rheometer, and mixed at 160~180°C and 60~80rpm for 10~12min to obtain pre-modified polyethylene.

[0014] As an optimization, the process parameters of the twin-screw extruder in step (3) are: zone 1 temperature 180~185℃, zone 2 temperature 185~190℃, zone 3 temperature 190~195℃, zone 4 temperature 195~200℃, zone 5 temperature 200~205℃, and screw speed 180~200r / min.

[0015] As an optimization, the preparation process of the pre-irradiated polyethylene is as follows: polyethylene is irradiated with 60 Coγ rays were irradiated at room temperature with an absorbed dose of 25~75kGy to produce pre-irradiated polyethylene.

[0016] As an optimization, the nano-cerium dioxide model is XH-CeO2-40, which was purchased from Shanghai Xiaohuang Nano Technology Co., Ltd.

[0017] As an optimization, the polyethylene is low-density polyethylene powder purchased from Shanghai Myrel Biochemical Technology Co., Ltd., with a weight-average molecular weight of 3000-4000.

[0018] Compared with the prior art, the present invention has the following beneficial effects: When preparing the rare earth modified polymer material, the present invention comprises the following steps: reacting nano cerium dioxide with 2-chloroethyltriethoxysilane to obtain pre-modified nano cerium dioxide; subjecting the pre-modified nano cerium dioxide to a quaternization reaction with 7-(diethylamino)coumarin to generate modified nano cerium dioxide; melt grafting pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine to obtain pre-modified polyethylene; reacting the pre-modified polyethylene with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to obtain modified polyethylene; and melt blending the modified polyethylene and the modified nano cerium dioxide to obtain the rare earth modified polymer material.

[0019] First, nano-cerium dioxide and 2-chloroethyltriethoxysilane are reacted to prepare pre-modified nano-cerium dioxide, and the nano-cerium dioxide is surface-modified with chloromethyl (methyl) diethoxysilane to improve the compatibility of nano-cerium dioxide with polyethylene. The cerium element can promote the formation of a carbon layer and can also block the combustion reaction by capturing free radicals, thereby improving the flame retardant properties of the material. At the same time, nano-cerium dioxide can reflect and scatter a large amount of ultraviolet light and absorb some ultraviolet light, thereby improving the anti-aging properties of the material. The pre-modified nano-cerium dioxide is reacted with 7-(diethylamino) coumarin to generate modified nano-cerium dioxide. The pre-modified nano-cerium dioxide and 7-(diethylamino) coumarin undergo a quaternization reaction to produce a quaternary ammonium salt with good antibacterial properties. At the same time, the coumarin group is introduced into the material, and the coumarin can absorb ultraviolet light, further improving the anti-aging properties of the material.

[0020] Secondly, pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine are reacted to produce pre-modified polyethylene, which is then melt-grafted onto the polyethylene to introduce phosphorus, thereby improving the flame retardant properties of the material. The triazine structure in 2-(allyloxy)-4,6-dichloro-1,3,5-triazine contains a large amount of nitrogen, which synergizes with the phosphorus to further improve the flame retardant properties of the material. The pre-modified polyethylene is reacted with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to produce modified polyethylene. The chlorine on 2-(allyloxy)-4,6-dichloro-1,3,5-triazine reacts with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to generate hindered amines, which can capture free radicals and synergize with cerium dioxide and coumarin to improve the material's anti-aging properties.

[0021] Finally, the modified polyethylene and modified nano-cerium dioxide were melt-blended to prepare a rare earth modified polymer material. The phosphonic acid on the modified polyethylene and the quaternary ammonium cation on the modified nano-cerium dioxide were electrostatically bonded, thereby improving the mechanical properties of the material. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described 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 are within the scope of protection of the present invention.

[0023] Example 1: A method for preparing a rare earth modified polymer material comprises the following steps: (1) 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution were mixed in a mass ratio of 1:10, ultrasonically dispersed for 20 minutes, and nano-cerium dioxide with a mass of 0.1 times that of 2-chloroethyltriethoxysilane was added, mixed evenly, ultrasonically dispersed for 30 minutes, stirred at 75°C, 200r / min for 8 hours, filtered and washed twice with anhydrous ethanol, and vacuum dried at 60°C for 10 hours to obtain pre-modified nano-cerium dioxide; pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin, and N,N-dimethylformamide were mixed in a mass ratio of 1:1.2:15, stirred at 50°C, 200r / min for 10 hours, and N,N-dimethylformamide was removed by rotary evaporation. The resulting product was washed twice with anhydrous ethanol and vacuum dried at 40°C for 1 hour to obtain modified nano-cerium dioxide; (2) In air atmosphere, polyethylene 60 Coγ-rays were irradiated at room temperature with an absorbed dose of 25 kGy to obtain pre-irradiated polyethylene; under a nitrogen atmosphere, the pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly in a mass ratio of 1:0.02:0.04, added to a torque rheometer, and mixed at 160°C and 60 rpm for 10 minutes to obtain pre-modified polyethylene; the pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:0.1:1 5. Mix evenly, stir and react at 40°C, 200r / min for 2h, add 20wt% sodium hydroxide aqueous solution (0.2 times the mass of pre-modified polyethylene) at a uniform rate of 5ml / min, stir and react at 80°C, 200r / min for 6h, cool to room temperature, filter, rotary evaporate the filtrate to remove N,N-dimethylformamide, add deionized water (20 times the mass of pre-modified polyethylene), stir at 300r / min for 10min at room temperature, filter and wash with deionized water twice, and vacuum dry at 60°C for 10h to obtain modified polyethylene; (3) The modified polyethylene and modified nano-cerium dioxide were mixed evenly in a mass ratio of 1:0.04, and added into a twin-screw extruder. The temperature of zone 1 was 180°C, the temperature of zone 2 was 185°C, the temperature of zone 3 was 190°C, the temperature of zone 4 was 195°C, the temperature of zone 5 was 200°C, the screw speed was 180 r / min, melt extrusion was performed, injection molding was performed, cooled to room temperature, demolded and taken out to obtain a rare earth modified polymer material.

[0024] Example 2: A method for preparing a rare earth modified polymer material comprises the following steps: (1) 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution were mixed in a mass ratio of 1:11, ultrasonically dispersed for 30 minutes, and nano-cerium dioxide with a mass of 0.15 times that of 2-chloroethyltriethoxysilane was added, mixed evenly, ultrasonically dispersed for 35 minutes, stirred at 78°C, 250r / min for 9 hours, filtered and washed with anhydrous ethanol three times, and vacuum dried at 65°C for 11 hours to obtain pre-modified nano-cerium dioxide; pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin, and N,N-dimethylformamide were mixed in a mass ratio of 1:1.3:18, stirred at 55°C, 250r / min for 11 hours, and N,N-dimethylformamide was removed by rotary evaporation. The resulting product was washed with anhydrous ethanol three times and vacuum dried at 45°C for 11 hours to obtain modified nano-cerium dioxide; (2) In air atmosphere, polyethylene 60 Coγ-rays were irradiated at room temperature with an absorbed dose of 50 kGy to obtain pre-irradiated polyethylene; under a nitrogen atmosphere, the pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were uniformly mixed in a mass ratio of 1:0.03:0.05, added to a torque rheometer, and mixed at 170°C and 70 rpm for 11 minutes to obtain pre-modified polyethylene; the pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:0.15:1 8. Mix well, stir and react at 50°C, 250r / min for 3h, add 20wt% sodium hydroxide aqueous solution (0.25 times the mass of pre-modified polyethylene) at a uniform rate of 5ml / min, stir and react at 90°C, 250r / min for 7h, cool to room temperature, filter, rotary evaporate the filtrate to remove N,N-dimethylformamide, add deionized water (25 times the mass of pre-modified polyethylene), stir at 400r / min for 15min at room temperature, filter and wash with deionized water 3 times, and vacuum dry at 65°C for 11h to obtain modified polyethylene; (3) The modified polyethylene and modified nano-cerium dioxide were mixed evenly in a mass ratio of 1:0.05 and added into a twin-screw extruder. The temperature of zone 1 was 183°C, the temperature of zone 2 was 188°C, the temperature of zone 3 was 193°C, the temperature of zone 4 was 198°C, the temperature of zone 5 was 203°C, the screw speed was 190 r / min, melt extrusion was performed, injection molding was performed, cooled to room temperature, demolded and taken out to obtain a rare earth modified polymer material.

[0025] Example 3: A method for preparing a rare earth modified polymer material comprises the following steps: (1) 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution were mixed in a mass ratio of 1:12, ultrasonically dispersed for 40 minutes, and nano-cerium dioxide with a mass of 0.2 times that of 2-chloroethyltriethoxysilane was added, mixed evenly, ultrasonically dispersed for 40 minutes, stirred at 80°C, 300r / min for 10 hours, filtered and washed with anhydrous ethanol 4 times, and vacuum dried at 70°C for 12 hours to obtain pre-modified nano-cerium dioxide; pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin, and N,N-dimethylformamide were mixed in a mass ratio of 1:1.4:20, stirred at 60°C, 300r / min for 12 hours, and N,N-dimethylformamide was removed by rotary evaporation. The resulting product was washed with anhydrous ethanol 4 times and vacuum dried at 50°C for 12 hours to obtain modified nano-cerium dioxide; (2) In air atmosphere, polyethylene 60 Coγ-rays were irradiated at room temperature with an absorbed dose of 75 kGy to obtain pre-irradiated polyethylene; under a nitrogen atmosphere, the pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly in a mass ratio of 1:0.04:0.06, added to a torque rheometer, and mixed at 180 ° C and 80 rpm for 12 minutes to obtain pre-modified polyethylene; the pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:0.2:20 The mixture was mixed evenly, stirred and reacted at 60°C and 300 r / min for 4 h, and a 20 wt% sodium hydroxide aqueous solution (0.3 times the mass of the pre-modified polyethylene) was uniformly added dropwise at a rate of 5 ml / min, stirred and reacted at 100°C and 300 r / min for 8 h, cooled to room temperature, filtered, and the filtrate was rotary evaporated to remove N, N-dimethylformamide, and deionized water (30 times the mass of the pre-modified polyethylene) was added, stirred at 500 r / min for 20 min at room temperature, filtered, washed with deionized water 4 times, and vacuum dried at 70°C for 12 h to obtain modified polyethylene; (3) The modified polyethylene and modified nano-cerium dioxide were mixed evenly in a mass ratio of 1:0.06, and added into a twin-screw extruder. The temperature of zone 1 was 185°C, the temperature of zone 2 was 190°C, the temperature of zone 3 was 195°C, the temperature of zone 4 was 200°C, the temperature of zone 5 was 205°C, the screw speed was 200 r / min, melt extrusion was performed, injection molding was performed, cooled to room temperature, demolded and taken out to obtain a rare earth modified polymer material.

[0026] Comparative Example 1: The preparation method of the rare earth modified polymer material of Comparative Example 1 differs from that of Example 2 in that step (1) is different. Step (1) is modified as follows: 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution are mixed uniformly in a mass ratio of 1:11, ultrasonically dispersed for 30 minutes, nano-cerium dioxide with a mass of 0.15 times that of 2-chloroethyltriethoxysilane is added, mixed uniformly, ultrasonically dispersed for 35 minutes, stirred at 78°C and 250r / min for 9 hours, filtered and washed with anhydrous ethanol three times, and vacuum dried at 65°C for 11 hours to obtain modified nano-cerium dioxide. The remaining steps are the same as those of Example 2.

[0027] Comparative Example 2: The method for preparing the rare earth modified polymer material of Comparative Example 2 differs from that of Example 2 in that step (1) is omitted and step (3) is modified as follows: the modified polyethylene is added to a twin-screw extruder, the temperature of zone 1 is 183°C, the temperature of zone 2 is 188°C, the temperature of zone 3 is 193°C, the temperature of zone 4 is 198°C, the temperature of zone 5 is 203°C, the screw speed is 190 r / min, melt extrusion is performed, injection molding is performed, cooling to room temperature, and demolding is performed to obtain the rare earth modified polymer material. The remaining steps are the same as those of Example 2.

[0028] Comparative Example 3: The preparation method of the rare earth modified polymer material of Comparative Example 3 differs from that of Example 2 in that step (2) is omitted and step (3) is modified as follows: polyethylene and modified nano-cerium dioxide are uniformly mixed in a mass ratio of 1:0.05, added to a twin-screw extruder, the temperature of zone 1 is 183°C, the temperature of zone 2 is 188°C, the temperature of zone 3 is 193°C, the temperature of zone 4 is 198°C, the temperature of zone 5 is 203°C, the screw speed is 190 r / min, melt extrusion is performed, injection molding is performed, cooling to room temperature, demolding and removal are performed to obtain a rare earth modified polymer material. The remaining steps are the same as those of Example 2.

[0029] Comparative Example 4: The difference between the preparation method of the rare earth modified polymer material of Comparative Example 4 and Example 2 lies in the difference in step (2). Step (2) is modified as follows: In an air atmosphere, polyethylene is 60Coγ-rays were irradiated at room temperature with an absorbed dose of 50 kGy to obtain pre-irradiated polyethylene; under a nitrogen atmosphere, the pre-irradiated polyethylene and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly in a mass ratio of 1:0.05, added to a torque rheometer, and mixed at 170°C and 70 rpm for 11 minutes to obtain pre-modified polyethylene; the pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:0.15:18. The mixture was stirred at 50°C and 250 rpm for 3 hours. A 20 wt% aqueous sodium hydroxide solution (0.25 times the mass of the pre-modified polyethylene) was then added dropwise at a rate of 5 ml / min. The mixture was stirred at 90°C and 250 rpm for 7 hours. The mixture was cooled to room temperature and filtered. The filtrate was rotary evaporated to remove N,N-dimethylformamide. Deionized water (25 times the mass of the pre-modified polyethylene) was added. The mixture was stirred at 400 rpm at room temperature for 15 minutes. The mixture was filtered and washed three times with deionized water. The mixture was then vacuum dried at 65°C for 11 hours to produce the modified polyethylene. The remaining steps were the same as in Example 2.

[0030] Comparative Example 5: The difference between the preparation method of the rare earth modified polymer material of Comparative Example 5 and Example 2 lies in the difference in step (2). Step (2) is modified as follows: In an air atmosphere, polyethylene is 60 Co γ-ray irradiation was performed at room temperature with an absorbed dose of 50 kGy to produce pre-irradiated polyethylene. Under a nitrogen atmosphere, the pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were uniformly mixed in a mass ratio of 1:0.03:0.05 and mixed at 170°C and 70 rpm for 11 minutes to produce modified polyethylene. The remaining steps were the same as in Example 2.

[0031] Test Example 1: Flame retardant performance test: The rare earth modified polymer materials obtained in the examples and comparative examples were made into standard specimens according to GB / T2406.2-2009, and the limiting oxygen index was tested.

[0032] The results are shown in Table 1.

[0033] Table 1

[0034] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the rare earth modified polymer material prepared in the present invention has good flame retardant properties.

[0035] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that cerium can promote the formation of a carbon layer and can also block the combustion reaction by capturing free radicals, thereby improving the flame retardant properties of the rare earth modified polymer material.

[0036] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Examples 3 to 4, indicating that melt-grafting vinylphosphonic acid and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine onto polyethylene and introducing phosphorus into the material improve the flame retardant properties of the rare earth-modified polymer material; the triazine structure in 2-(allyloxy)-4,6-dichloro-1,3,5-triazine contains a large amount of nitrogen, which synergistically flame retards with phosphorus, further improving the flame retardant properties of the rare earth-modified polymer material.

[0037] Test Example 2: Tensile strength and anti-aging performance test: Tensile strength test method: The rare earth modified polymer materials obtained in each example and the comparative example were made into test specimens of 10 cm×10 mm×1 mm, and tested with reference to GB / T1040-2006 at a tensile speed of 10 mm / min to test the tensile strength M.

[0038] Anti-aging performance test method: The rare earth modified polymer materials obtained in each embodiment and the comparative example were made into test samples of 10 cm × 10 mm × 1 mm, and UV aging tests were carried out using a UVA-340 lamp according to GB / T16422.3-2022. The aging time was 360 h, and one cycle was 12 h. The cycle test conditions were: the irradiance was 0.76 W / m 2 , blackboard temperature is 60℃, exposure is 8 hours, condensation is 4 hours; test the tensile strength N again, and calculate the performance degradation rate = 1-N / M×100%. Test the tensile strength N again, and calculate the performance degradation rate = 1-N / M×100%.

[0039] The results are shown in Table 2.

[0040] Table 2

[0041] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 2, it can be found that the rare earth modified polymer material prepared in the present invention has good tensile strength and anti-aging properties.

[0042] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Examples 1 to 4, indicating that the modified polyethylene and the modified nano-cerium dioxide are melt-blended, and the phosphonic acid on the modified polyethylene and the quaternary ammonium cation on the modified nano-cerium dioxide are electrostatically bonded, thereby improving the mechanical properties of the rare earth modified polymer material.

[0043] By comparison, the performance degradation rates of Examples 1 to 3 are less than that of Comparative Example 1, indicating that the pre-modified nano-cerium dioxide and 7-(diethylamino) coumarin undergo a quaternization reaction to generate modified nano-cerium dioxide, and coumarin groups are introduced into the material. Coumarin can absorb ultraviolet light, thereby improving the anti-aging performance of the rare earth modified polymer material.

[0044] By comparison, the performance degradation rate of Examples 1 to 3 is less than that of Comparative Example 2, which shows that nano-cerium dioxide can reflect and scatter a large amount of ultraviolet light. At the same time, it can also absorb part of the ultraviolet light, and cooperate with the coumarin group to resist aging, further improving the anti-aging performance of rare earth modified polymer materials.

[0045] By comparison, the performance degradation rates of Examples 1 to 3 are less than those of Comparative Examples 3 and 5, indicating that the modified polyethylene is prepared by reacting the pre-modified polyethylene with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and the chlorine on 2-(allyloxy)-4,6-dichloro-1,3,5-triazine reacts with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to form a hindered amine structure, which can capture free radicals, thereby improving the anti-aging performance of the rare earth modified polymer material.

[0046] Test Example 3: Antibacterial testing: According to GB / T31402-2023 "Determination of antibacterial activity on the surface of plastics and other non-porous materials", the antibacterial rate against Escherichia coli and Staphylococcus aureus was tested.

[0047] The results are shown in Table 3.

[0048] Table 3

[0049] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 3, it can be found that the rare earth modified polymer material prepared by the present invention has good antibacterial properties.

[0050] By comparison, the antibacterial properties of Examples 1 to 3 are greater than those of Comparative Examples 1 to 2, indicating that the pre-modified nano-cerium dioxide undergoes a quaternization reaction with 7-(diethylamino)coumarin, and the generated quaternary ammonium salt has good antibacterial properties, thereby improving the antibacterial properties of the rare earth modified polymer material.

[0051] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A rare earth modified polymer material, characterized in that: The rare earth modified polymer material is prepared by melt-blending modified polyethylene and modified nano-cerium dioxide; The modified polyethylene is prepared by reacting pre-modified polyethylene with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; The pre-modified polyethylene is prepared by melt grafting pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine; The modified nano-cerium dioxide is prepared by a quaternization reaction between pre-modified nano-cerium dioxide and 7-(diethylamino)coumarin; The pre-modified nano-cerium dioxide is prepared by reacting nano-cerium dioxide with 2-chloroethyltriethoxysilane.

2. A method for preparing a rare earth modified polymer material, characterized in that: The method comprises the following preparation steps: (1) Pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:(1.2-1.4):(15-20), stirred at 50-60°C and 200-300 r / min for 10-12 h, and N,N-dimethylformamide was removed by rotary evaporation. The obtained product was washed with anhydrous ethanol 2-4 times and vacuum dried at 40-50°C for 10-12 h to obtain modified nano-cerium dioxide; (2) Pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1: (0.1~0.2): (15~20), stirred at 40~60℃, 200~300r / min for 2~4h, 20wt% sodium hydroxide aqueous solution (0.2~0.3 times the mass of pre-modified polyethylene) was added dropwise at a rate of 5ml / min, stirred at 80~100℃, 200~300r / min for 6~8h, cooled to room temperature, filtered, and the filtrate was rotary evaporated to remove N,N-dimethylformamide, deionized water (20~30 times the mass of pre-modified polyethylene) was added, stirred at 300~500r / min for 10~20min at room temperature, filtered, washed with deionized water 2~4 times, and vacuum dried at 60~70℃ for 10~12h to obtain modified polyethylene; (3) The modified polyethylene and modified nano-cerium dioxide are mixed evenly in a mass ratio of 1: (0.04-0.06), added into a twin-screw extruder, melt-extruded, injection-molded, cooled to room temperature, demolded and taken out to obtain a rare earth modified polymer material.

3. The method for preparing a rare earth modified polymer material according to claim 2, characterized in that: The preparation process of the pre-modified nano-cerium dioxide in step (1) is as follows: 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution are mixed uniformly in a mass ratio of 1: (10~12), ultrasonically dispersed for 20~40min, nano-cerium dioxide with a mass of 0.1~0.2 times that of 2-chloroethyltriethoxysilane is added, mixed uniformly, ultrasonically dispersed for 30~40min, stirred at 75~80℃ and 200~300r / min for 8~10h, filtered and washed with anhydrous ethanol 2~4 times, and vacuum dried at 60~70℃ for 10~12h to obtain pre-modified nano-cerium dioxide.

4. The method for preparing a rare earth modified polymer material according to claim 2, characterized in that: The preparation process of the pre-modified polyethylene in step (2) is as follows: under a nitrogen atmosphere, pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine are uniformly mixed in a mass ratio of 1: (0.02~0.04): (0.04~0.06), added to a torque rheometer, and mixed at 160~180°C and 60~80rpm for 10~12min to obtain pre-modified polyethylene.

5. The method for preparing a rare earth modified polymer material according to claim 2, characterized in that: The process parameters of the twin-screw extruder in step (3) are as follows: zone 1 temperature 180~185°C, zone 2 temperature 185~190°C, zone 3 temperature 190~195°C, zone 4 temperature 195~200°C, zone 5 temperature 200~205°C, and screw speed 180~200r / min.

6. The method for preparing a rare earth modified polymer material according to claim 4, characterized in that: The preparation process of the pre-irradiated polyethylene is as follows: in an air atmosphere, polyethylene is 60 Coγ rays were irradiated at room temperature with an absorbed dose of 25~75kGy to produce pre-irradiated polyethylene.

7. The method for preparing a rare earth modified polymer material according to claim 6, characterized in that: The polyethylene is low-density polyethylene powder with a weight-average molecular weight of 3000-4000.

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