Rare earth modified high molecular material and preparation method thereof

Abstract

The application discloses a rare earth modified polymer material and a preparation method thereof, and relates to the technical field of polymer materials. In the preparation of the rare earth modified polymer material, pre-modified nano cerium dioxide is prepared by reacting nano cerium dioxide and 2-chloroethyl triethoxysilane; modified nano cerium dioxide is generated by quaternary ammonium reaction of the pre-modified nano cerium dioxide and 7-(diethylamino) coumarin; pre-modified polyethylene is prepared by melt grafting of pre-irradiated polyethylene, vinyl phosphonic acid and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine; modified polyethylene is prepared by reacting the pre-modified polyethylene and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; and the rare earth modified polymer material is prepared by melt blending of the modified polyethylene and the modified nano cerium dioxide. The rare earth modified polymer material prepared by the application has good flame retardant performance, antibacterial performance, tensile strength and anti-aging performance.

Description

TECHNICAL FIELD

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

[0002] Rare earth refers to the collective name of 17 chemical elements in the periodic table of elements ⅢB group, yttrium and lanthanide elements, etc., and the rare earth elements have unique 4f electron layer energy level structure, showing unique electricity, magnetism, light and catalysis, etc. Physical and chemical properties, and have important application value in functional materials, often referred to as "industrial gold" or "industrial vitamin". Among the 17 rare earth elements, the abundance of cerium in the earth's crust is the highest, reaching 68 ppm, because Ce is rich in resources and easy to extract, so Ce is relatively cheap than other rare earth, also become one of the earliest practical use of rare earth elements.

[0003] Cerium dioxide is a widely used and cost-effective rare earth oxide material, widely used in ultraviolet absorber, automobile exhaust catalyst, electronic ceramics, glass coating and luminescent material, etc. Nano cerium dioxide can absorb and shield ultraviolet rays, and has good anti-aging performance. At the same time, cerium dioxide has the characteristics of catalyzing esterification and dehydrogenation, which can promote the carbonization of polymer matrix, so it is often used as a synergist of flame retardant system.

[0004] Polyethylene has many excellent properties such as light weight, low cost, heat resistance, easy processing, good chemical corrosion resistance, etc., so it is widely used in medical equipment, pipeline, chemical industry, agriculture, ship and other fields. Polyethylene is a long-chain macromolecule composed of carbon and hydrogen elements, so it has the disadvantage of flammability. Moreover, polyethylene releases a large amount of heat during combustion, accompanied by smoke and dripping, which can easily cause the spread of combustion and cause large-area fire in a short time. At the same time, polyethylene materials are usually used outdoors and are exposed to sunlight all year round, which can easily cause material aging. Light aging can cause polyethylene chain scission and branching, leading to polyethylene degradation and thus a significant decrease in the mechanical properties of polyethylene, affecting the normal use of the material. Therefore, the present application prepares a rare earth modified high polymer material which has good flame retardant and anti-aging properties. SUMMARY

[0005] The present application aims to provide a rare earth modified high polymer material and a preparation method thereof to solve the problems in the prior art.

[0006] In order to solve the above technical problems, the present application provides the following technical scheme:

[0007] A rare earth modified high polymer material, which is prepared by melt blending modified polyethylene and modified nano cerium dioxide.

[0008] As an optimization, the modified polyethylene is prepared by reacting a pre-modified polyethylene and N-butyl-2, 2, 6, 6-tetramethyl-4-piperidinamine.

[0009] As an optimization, the pre-modified polyethylene is prepared by melt grafting a pre-irradiated polyethylene, vinyl phosphonic acid, and 2-(allyloxy)-4, 6-dichloro-1, 3, 5-triazine.

[0010] As an optimization, the modified nanometer cerium dioxide is prepared by quaternary ammonium reaction of a pre-modified nanometer cerium dioxide and 7-(diethylamino) coumarin.

[0011] As an optimization, the pre-modified nanometer cerium dioxide is prepared by reacting nanometer cerium dioxide and 2-chloroethyl triethoxysilane.

[0012] A rare earth modified high polymer material and a preparation method thereof, comprising the following preparation steps:

[0013] (1) uniformly mixing pre-modified nanometer cerium dioxide, 7-(diethylamino) coumarin, and N, N-dimethylformamide according to a mass ratio of 1: (1.2-1.4): (15-20), stirring at 200-300 r / min at 50-60 °C for 10-12 h, removing N, N-dimethylformamide by rotary evaporation, washing the obtained product with anhydrous ethanol for 2-4 times, and vacuum drying at 40-50 °C for 10-12 h to prepare modified nanometer cerium dioxide;

[0014] (2) uniformly mixing pre-modified polyethylene, N-butyl-2, 2, 6, 6-tetramethyl-4-piperidinamine, and N, N-dimethylformamide according to a mass ratio of 1: (0.1-0.2): (15-20), stirring at 200-300 r / min at 40-60 °C for 2-4 h, uniformly dropping 20 wt% sodium hydroxide aqueous solution at a rate of 5 ml / min and in an amount of 0.2-0.3 times the mass of the pre-modified polyethylene, stirring at 200-300 r / min at 80-100 °C for 6-8 h, cooling to room temperature, filtering, removing N, N-dimethylformamide by rotary evaporation of the obtained filtrate, adding deionized water in an amount of 20-30 times the mass of the pre-modified polyethylene, stirring at 300-500 r / min at room temperature for 10-20 min, filtering and washing with deionized water for 2-4 times, and vacuum drying at 60-70 °C for 10-12 h to prepare modified polyethylene;

[0015] (3) uniformly mixing modified polyethylene and modified nanometer cerium dioxide according to a mass ratio of 1: (0.04-0.06), feeding into a twin-screw extruder, melt extruding, injection molding, cooling to room temperature, demolding, and taking out to prepare a rare earth modified high polymer material.

[0016] As optimization, the preparation process of the pre-modified nanometer cerium dioxide in step (1) is as follows: 2-chloroethyl triethoxysilane and 90wt% ethanol aqueous solution are uniformly mixed in a mass ratio of 1: (10-12), ultrasonic dispersion is carried out for 20-40 min, 2-chloroethyl triethoxysilane with a mass of 0.1-0.2 times of the nanometer cerium dioxide is added, uniform mixing is carried out, ultrasonic dispersion is carried out for 30-40 min, stirring reaction is carried out at 75-80℃ and 200-300 r / min for 8-10 h, filtration is carried out, and the pre-modified nanometer cerium dioxide is prepared by washing with anhydrous ethanol for 2-4 times and vacuum drying at 60-70℃ for 10-12 h.

[0017] As optimization, the preparation process of the pre-modified polyethylene in step (2) is as follows: under a nitrogen atmosphere, pre-irradiated polyethylene, ethylene phosphonic 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), and then are added into a torque rheometer, and mixing is carried out at 160-180℃ and 60-80 rpm for 10-12 min, so as to prepare the pre-modified polyethylene.

[0018] As optimization, the process parameters of the double-screw extruder in step (3) are as follows: the temperature of the first zone is 180-185℃, the temperature of the second zone is 185-190℃, the temperature of the third zone is 190-195℃, the temperature of the fourth zone is 195-200℃, the temperature of the fifth zone is 200-205℃, and the screw rotation speed is 180-200 r / min.

[0019] As optimization, the preparation process of the pre-irradiated polyethylene is as follows: under an air atmosphere, polyethylene is irradiated by Co gamma rays at room temperature, and the absorbed dose is 25-75 kGy, so as to prepare the pre-irradiated polyethylene. 60 Co gamma rays at room temperature, and the absorbed dose is 25-75 kGy, so as to prepare the pre-irradiated polyethylene.

[0020] As optimization, the nanometer cerium dioxide is of the type XH-CeO2-40, and is purchased from Shanghai Xiaohuang Nanometer Technology Co., Ltd.

[0021] As optimization, the polyethylene is low-density polyethylene powder, and is purchased from Shanghai Maier Biochemical Technology Co., Ltd.

[0022] Compared with the prior art, the present application has the following beneficial effects:

[0023] The application is characterized in that: in the preparation of the rare earth modified high polymer material, the pre-modified nano cerium dioxide is prepared by the reaction of nano cerium dioxide and 2-chloroethyl triethoxysilane; the modified nano cerium dioxide is generated by the quaternary ammonium reaction of the pre-modified nano cerium dioxide and 7-(diethylamino) coumarin; the pre-modified polyethylene is prepared by the melt grafting of pre-irradiated polyethylene, vinyl phosphonic acid and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine; the modified polyethylene is prepared by the reaction of the pre-modified polyethylene and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; and the rare earth modified high polymer material is prepared by the melt blending of the modified polyethylene and the modified nano cerium dioxide.

[0024] Firstly, the pre-modified nano cerium dioxide is prepared by the reaction of nano cerium dioxide and 2-chloroethyl triethoxysilane, and the surface of the nano cerium dioxide is modified by chloromethyl (methyl) diethoxysilane to improve the compatibility of the nano cerium dioxide and the polyethylene; the cerium element can promote the formation of the carbon layer and block the combustion reaction by capturing free radicals to improve the flame retardant performance of the material; meanwhile, the nano cerium dioxide can reflect and scatter a large amount of ultraviolet light and absorb part of the ultraviolet light to improve the anti-aging performance of the material; the modified nano cerium dioxide is generated by the reaction of the pre-modified nano cerium dioxide and 7-(diethylamino) coumarin, and the pre-modified nano cerium dioxide and 7-(diethylamino) coumarin undergo the quaternary ammonium reaction to generate quaternary ammonium salt with good antibacterial performance, and the coumarin group is introduced into the material, and the coumarin can absorb ultraviolet light to further improve the anti-aging performance of the material.

[0025] Secondly, the pre-modified polyethylene is prepared by the reaction of pre-irradiated polyethylene, vinyl phosphonic acid and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine, and the phosphorus element is introduced into the polyethylene by melt grafting to improve the flame retardant performance of the material, and the triazine structure in the 2-(allyloxy)-4,6-dichloro-1,3,5-triazine contains a large amount of nitrogen element which cooperates with the phosphorus element to further improve the flame retardant performance of the material; the modified polyethylene is prepared by the reaction of the pre-modified polyethylene and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the chlorine on the 2-(allyloxy)-4,6-dichloro-1,3,5-triazine reacts with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to generate a hindered amine which can capture free radicals, and cooperates with the cerium dioxide and the coumarin to improve the anti-aging performance of the material.

[0026] Finally, the rare earth modified high polymer material is prepared by the melt blending of the modified polyethylene and the modified nano cerium dioxide, and the phosphonic acid on the modified polyethylene is electrostatically combined with the quaternary ammonium cation on the modified nano cerium dioxide to improve the mechanical performance of the material. DETAILED DESCRIPTION

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1:

[0029] A method for preparing a rare earth modified polymer material includes the following preparation steps:

[0030] (1) 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:10, ultrasonically dispersed for 20 min, 0.1 times the mass of 2-chloroethyltriethoxysilane nano-cerium dioxide were added, mixed evenly, ultrasonically dispersed for 30 min, stirred at 75℃ and 200 r / min for 8 h, filtered and washed twice with anhydrous ethanol, and vacuum dried at 60℃ for 10 h to obtain pre-modified nano-cerium dioxide; pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.2:15, stirred at 50℃ and 200 r / min for 10 h, N,N-dimethylformamide was removed by rotary evaporation, the obtained product was washed twice with anhydrous ethanol, and vacuum dried at 40℃ for 1 h to obtain modified nano-cerium dioxide;

[0031] (2) In an air atmosphere, polyethylene is used 60 Pre-irradiated polyethylene was prepared by irradiating with Co-γ rays at room temperature with an absorbed dose of 25 kGy. Pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly at a mass ratio of 1:0.02:0.04 under a nitrogen atmosphere and added to a torque rheometer. The mixture was then stirred at 160°C and 60 rpm for 10 min to prepare pre-modified polyethylene. Pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed at a mass ratio of 1:0.1:1. 5. Mix thoroughly and stir at 200 r / min for 2 h at 40 °C. Add 20 wt% sodium hydroxide aqueous solution (0.2 times the mass of pre-modified polyethylene) dropwise at a rate of 5 ml / min. Stir at 200 r / min for 6 h at 80 °C. Cool to room temperature and filter. Remove N,N-dimethylformamide from the filtrate by rotary evaporation. Add deionized water (20 times the mass of pre-modified polyethylene) and stir at 300 r / min for 10 min at room temperature. Filter and wash twice with deionized water. Vacuum dry at 60 °C for 10 h to obtain modified polyethylene.

[0032] (3) Mix the modified polyethylene and modified nano-cerium dioxide at a mass ratio of 1:0.04, add them to a twin-screw extruder, set the temperature of zone 1 to 180℃, zone 2 to 185℃, zone 3 to 190℃, zone 4 to 195℃, zone 5 to 200℃, and screw speed to 180r / min, melt extrusion, injection molding, cool to room temperature, demold and take out to obtain rare earth modified polymer material.

[0033] Example 2:

[0034] A method for preparing a rare earth modified polymer material includes the following preparation steps:

[0035] (1) 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:11, ultrasonically dispersed for 30 min, and nano-cerium dioxide with a mass of 0.15 times that of 2-chloroethyltriethoxysilane was added. The mixture was mixed evenly, ultrasonically dispersed for 35 min, stirred at 78℃ and 250 r / min for 9 h, filtered and washed 3 times with anhydrous ethanol, and vacuum dried at 65℃ for 11 h to obtain pre-modified nano-cerium dioxide; pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.3:18, stirred at 55℃ and 250 r / min for 11 h, N,N-dimethylformamide was removed by rotary evaporation, the product was washed 3 times with anhydrous ethanol, and vacuum dried at 45℃ for 11 h to obtain modified nano-cerium dioxide;

[0036] (2) In an air atmosphere, polyethylene is used 60 Pre-irradiated polyethylene was prepared by irradiating with Co-γ rays at room temperature with an absorbed dose of 50 kGy. Pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly at a mass ratio of 1:0.03:0.05 under a nitrogen atmosphere and added to a torque rheometer. The mixture was then stirred at 170°C and 70 rpm for 11 min to obtain pre-modified polyethylene. Pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed at a mass ratio of 1:0.15:1. 8. Mix thoroughly and stir at 50℃ and 250 r / min for 3 h. Add 0.25 times the mass of the pre-modified polyethylene in 20wt% sodium hydroxide aqueous solution at a rate of 5 ml / min. Stir at 90℃ and 250 r / min for 7 h. Cool to room temperature, filter, and remove N,N-dimethylformamide by rotary evaporation of the filtrate. Add 25 times the mass of the pre-modified polyethylene in deionized water, stir at 400 r / min for 15 min at room temperature, filter, wash three times with deionized water, and vacuum dry at 65℃ for 11 h to obtain modified polyethylene.

[0037] (3) Mix the modified polyethylene and modified nano-cerium dioxide at a mass ratio of 1:0.05, add them to a twin-screw extruder, set the temperature of zone 1 to 183℃, zone 2 to 188℃, zone 3 to 193℃, zone 4 to 198℃, zone 5 to 203℃, and screw speed to 190r / min, melt extrusion, injection molding, cool to room temperature, demold and take out to obtain rare earth modified polymer material.

[0038] Example 3:

[0039] A method for preparing a rare earth modified polymer material includes the following preparation steps:

[0040] (1) 2-chloroethyltriethoxysilane and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:12, ultrasonically dispersed for 40 min, 0.2 times the mass of 2-chloroethyltriethoxysilane nano-cerium dioxide were added, mixed evenly, ultrasonically dispersed for 40 min, stirred at 80℃ and 300 r / min for 10 h, filtered and washed 4 times with anhydrous ethanol, and vacuum dried at 70℃ for 12 h to obtain pre-modified nano-cerium dioxide; pre-modified nano-cerium dioxide, 7-(diethylamino)coumarin and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.4:20, stirred at 60℃ and 300 r / min for 12 h, N,N-dimethylformamide was removed by rotary evaporation, the obtained product was washed 4 times with anhydrous ethanol, and vacuum dried at 50℃ for 12 h to obtain modified nano-cerium dioxide;

[0041] (2) In an air atmosphere, polyethylene is used 60 Pre-irradiated polyethylene was prepared by irradiating with Co-γ rays at room temperature with an absorbed dose of 75 kGy. Pre-irradiated polyethylene, vinylphosphonic acid, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly at a mass ratio of 1:0.04:0.06 under a nitrogen atmosphere and added to a torque rheometer. The mixture was then stirred at 180°C and 80 rpm for 12 min to obtain pre-modified polyethylene. Pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and N,N-dimethylformamide were mixed at a mass ratio of 1:0.2:20. The mixture was thoroughly mixed and stirred at 60℃ and 300 r / min for 4 h. A 20 wt% sodium hydroxide aqueous solution, equal to 0.3 times the mass of the pre-modified polyethylene, was added dropwise at a rate of 5 ml / min. The mixture was stirred at 100℃ and 300 r / min for 8 h. After cooling to room temperature, the mixture was filtered. N,N-dimethylformamide was removed from the filtrate by rotary evaporation. Deionized water, equal to 30 times the mass of the pre-modified polyethylene, was added. The mixture was stirred at 500 r / min for 20 min at room temperature. The mixture was filtered and washed four times with deionized water. The mixture was then vacuum dried at 70℃ for 12 h to obtain the modified polyethylene.

[0042] (3) The modified polyethylene and the modified nanometer cerium dioxide are mixed uniformly at a mass ratio of 1:0.06, and are added into a double-screw extruder, the temperature of the first zone is 185°C, the temperature of the second zone is 190°C, the temperature of the third zone is 195°C, the temperature of the fourth zone is 200°C, the temperature of the fifth zone is 205°C, the screw rotation speed is 200 r / min, and then the material is melt-extruded, injection-molded, cooled to room temperature, demolded and taken out, so as to obtain the rare earth modified polymer material.

[0043] Comparative Example 1

[0044] The preparation method of the rare earth modified polymer material of Comparative Example 1 is different from that of Example 2 in that step (1) is modified, that is, 2-chloroethyl triethoxysilane and 90wt% ethanol aqueous solution are mixed uniformly at a mass ratio of 1:11, ultrasonic dispersion is performed for 30 min, 0.15 times the mass of nanometer cerium dioxide is added, and then the mixture is uniformly mixed and ultrasonic dispersed for 35 min, and then stirring reaction is performed at 78°C and 250 r / min for 9 h, and then the mixture is filtered, washed with anhydrous ethanol for 3 times, and dried at 65°C under vacuum for 11 h, so as to obtain the modified nanometer cerium dioxide. The other steps are the same as those of Example 2.

[0045] Comparative Example 2

[0046] The preparation method of the rare earth modified polymer material of Comparative Example 2 is different from that of Example 2 in that step (1) is not performed, and step (3) is modified, that is, the modified polyethylene is added into a double-screw extruder, the temperature of the first zone is 183°C, the temperature of the second zone is 188°C, the temperature of the third zone is 193°C, the temperature of the fourth zone is 198°C, the temperature of the fifth zone is 203°C, and the screw rotation speed is 190 r / min, and then the material is melt-extruded, injection-molded, cooled to room temperature, demolded and taken out, so as to obtain the rare earth modified polymer material. The other steps are the same as those of Example 2.

[0047] Comparative Example 3

[0048] The preparation method of the rare earth modified polymer material of Comparative Example 3 is different from that of Example 2 in that step (2) is not performed, and step (3) is modified, that is, the polyethylene and the modified nanometer cerium dioxide are mixed uniformly at a mass ratio of 1:0.05, and are added into a double-screw extruder, the temperature of the first zone is 183°C, the temperature of the second zone is 188°C, the temperature of the third zone is 193°C, the temperature of the fourth zone is 198°C, the temperature of the fifth zone is 203°C, and the screw rotation speed is 190 r / min, and then the material is melt-extruded, injection-molded, cooled to room temperature, demolded and taken out, so as to obtain the rare earth modified polymer material. The other steps are the same as those of Example 2.

[0049] Comparative Example 4

[0050] The preparation method of the rare earth modified polymer material of Comparative Example 4 is different from that of Example 2 in that step (2) is modified, that is, the polyethylene is treated with 60Pre-irradiated polyethylene was prepared by irradiating polyethylene under Co γ ray at room temperature with an absorbed dose of 50 kGy; the pre-irradiated polyethylene, 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly at a mass ratio of 1:0.05 under a nitrogen atmosphere, and then were added into a torque rheometer to be mixed at 170 ℃ and 70 rpm for 11 min 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 at a mass ratio of 1:0.15:18, and then were stirred at 50 ℃ and 250 r / min for 3 h; 20 wt% sodium hydroxide aqueous solution with a mass of 0.25 times that of the pre-modified polyethylene was added at a rate of 5 ml / min, and then the mixture was stirred at 90 ℃ and 250 r / min for 7 h; after cooling to room temperature, the mixture was filtered, and then N,N-dimethylformamide was removed from the obtained filtrate by rotary evaporation; deionized water with a mass of 25 times that of the pre-modified polyethylene was added, and then the mixture was stirred at room temperature and 400 r / min for 15 min; the mixture was filtered and washed with deionized water for 3 times, and then was dried at 65 ℃ under vacuum for 11 h to obtain modified polyethylene. The remaining steps were the same as those in Example 2.

[0051] Comparative Example 5:

[0052] The preparation method of the rare earth modified polymeric material in Comparative Example 5 is different from that in Example 2 in that step (2) is modified as follows: under an air atmosphere, polyethylene was irradiated by Co γ ray at room temperature with an absorbed dose of 50 kGy to obtain pre-irradiated polyethylene; the pre-irradiated polyethylene, 2-(allyloxy)-4,6-dichloro-1,3,5-triazine and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly at a mass ratio of 1:0.05:0.05 under a nitrogen atmosphere, and then were added into a torque rheometer to be mixed at 170 ℃ and 70 rpm for 11 min to obtain pre-modified polyethylene. The remaining steps were the same as those in Example 2. 60 Pre-irradiated polyethylene was prepared by irradiating polyethylene under Co γ ray at room temperature with an absorbed dose of 50 kGy; the pre-irradiated polyethylene, 2-(allyloxy)-4,6-dichloro-1,3,5-triazine were mixed uniformly at a mass ratio of 1:0.05 under a nitrogen atmosphere, and then were added into a torque rheometer to be mixed at 170 ℃ and 70 rpm for 11 min 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 at a mass ratio of 1:0.15:18, and then were stirred at 50 ℃ and 250 r / min for 3 h; 20 wt% sodium hydroxide aqueous solution with a mass of 0.25 times that of the pre-modified polyethylene was added at a rate of 5 ml / min, and then the mixture was stirred at 90 ℃ and 250 r / min for 7 h; after cooling to room temperature, the mixture was filtered, and then N,N-dimethylformamide was removed from the obtained filtrate by rotary evaporation; deionized water with a mass of 25 times that of the pre-modified polyethylene was added, and then the mixture was stirred at room temperature and 400 r / min for 15 min; the mixture was filtered and washed with deionized water for 3 times, and then was dried at 65 ℃ under vacuum for 11 h to obtain modified polyethylene. The remaining steps were the same as those in Example 2.

[0053] Test Example 1:

[0054] Flame Retardant Property Test:

[0055] According to GB / T2406.2-2009, the rare earth modified polymeric materials obtained in the examples and comparative examples were made into standard samples to test the limiting oxygen index.

[0056] The results are shown in Table 1.

[0057] Table 1

[0058]

[0059] From the experimental data of Examples 1-3 and Comparative Examples 1-5 in Table 1, it can be found that the rare earth modified polymeric material prepared by the present application has good flame retardant properties.

[0060] By comparison, the limiting oxygen index of examples 1-3 is greater than that of comparative example 2, which shows that the cerium element can promote the formation of carbon layer and also block the combustion reaction by capturing free radicals, thereby improving the flame retardant performance of the rare earth modified polymer material.

[0061] By comparison, the limiting oxygen index of examples 1-3 is greater than that of comparative examples 3-4, which shows that the ethylene-vinyl phosphonic acid and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine are melt-grafted on polyethylene to introduce phosphorus elements into the material, thereby improving the flame retardant performance 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 elements, which synergistically flame-retard with phosphorus elements, further improving the flame retardant performance of the rare earth modified polymer material.

[0062] Test example 2:

[0063] Tensile strength and anti-aging performance test:

[0064] Tensile strength test method: the rare earth modified polymer material obtained in each example and the comparative example are respectively made into a test sample with a size of 10cmx10mmx1mm, and the tensile strength M is tested by referring to GB / T1040-2006, and the tensile speed is 10mm / min.

[0065] Anti-aging performance test method: the rare earth modified polymer material obtained in each example and the comparative example are respectively made into a test sample with a size of 10cmx10mmx1mm, and the tensile strength N is tested by referring to GB / T16422.3-2022, and the ultraviolet aging test is carried out using a UVA-340 lamp, the aging time is 360h, 12h is a cycle period, and the cycle test conditions are: the radiation degree is 0.76W / m 2 , the blackboard temperature is 60℃, the exposure time is 8h, and the condensation time is 4h; the tensile strength N is tested again, and the performance decline rate =1-N / Mx100% is calculated.

[0066] The results are shown in Table 2.

[0067] Table 2

[0068]

[0069] From the experimental data comparison of examples 1-3 and comparative examples 1-5 in Table 2, it can be found that the rare earth modified polymer material prepared by the present application has good tensile strength and anti-aging performance.

[0070] By comparison, the tensile strength of examples 1-3 is greater than that of comparative examples 1-4, which indicates that the modified polyethylene is melt blended with the modified nanometer cerium dioxide, the phosphonic acid on the modified polyethylene and the quaternary ammonium cation on the modified nanometer cerium dioxide are electrostatically combined, and the mechanical properties of the rare earth modified high polymer material are improved.

[0071] By comparison, the performance degradation rate of examples 1-3 is less than that of comparative example 1, which indicates that the pre-modified nanometer cerium dioxide is subjected to a quaternary ammonium reaction with 7-(diethylamino) coumarin to generate modified nanometer cerium dioxide, and a coumarin group is introduced into the material, and the coumarin can absorb ultraviolet light, thereby improving the anti-aging performance of the rare earth modified high polymer material.

[0072] By comparison, the performance degradation rate of examples 1-3 is less than that of comparative example 2, which indicates that the nanometer cerium dioxide can reflect and scatter a large amount of ultraviolet light, and at the same time, can also absorb part of the ultraviolet light, and cooperates with the coumarin group to resist aging, thereby further improving the anti-aging performance of the rare earth modified high polymer material.

[0073] By comparison, the performance degradation rate of examples 1-3 is less than that of comparative examples 3 and 5, which indicates that the pre-modified polyethylene is reacted with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to generate modified polyethylene, and the chlorine on 2-(allyloxy)-4,6-dichloro-1,3,5-triazine is reacted with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to generate a hindered amine structure, which can capture free radicals, thereby improving the anti-aging performance of the rare earth modified high polymer material.

[0074] Test example 3:

[0075] Antibacterial test:

[0076] According to GB / T31402-2023 "Determination of Antibacterial Activity on the Surface of Plastic and Other Non-porous Materials", the antibacterial rate of Escherichia coli and Staphylococcus aureus is tested.

[0077] The results are shown in Table 3.

[0078] Table 3

[0079]

[0080] From the experimental data comparison of examples 1-3 and comparative examples 1-5 in Table 3, it can be found that the rare earth modified high polymer material prepared by the present application has good antibacterial performance.

[0081] By comparison, the antibacterial properties of examples 1-3 are greater than those of comparative examples 1-2, which indicates that the pre-modified nanometer cerium dioxide and 7-(diethylamino)coumarin undergo quaternary ammonium reaction, the generated quaternary ammonium salt has good antibacterial properties, and the antibacterial properties of the rare earth modified polymer material are improved.

[0082] The above detailed description of the specific embodiments has further detailed the purposes, technical solutions and beneficial effects of the present application, and it should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application, and any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A rare earth modified high molecular material, characterized by, The rare earth modified polymer material is prepared by melt blending of modified polyethylene and modified nanometer cerium dioxide; The modified polyethylene is prepared by reaction of pre-modified polyethylene and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; The pre-modified polyethylene is prepared by melt grafting of pre-irradiated polyethylene, vinyl phosphonic acid and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine; The modified nanometer cerium dioxide is prepared by quaternary ammonium reaction of pre-modified nanometer cerium dioxide and 7-(diethylamino)coumarin; The pre-modified nanometer cerium dioxide is prepared by reaction of nanometer cerium dioxide and 2-chloroethyl triethoxysilane.

2. A method for producing a rare earth-modified high molecular material, characterized by comprising the steps of: The preparation steps include: (1) uniformly mix pre-modified nanometer cerium dioxide, 7-(diethylamino)coumarin and N,N-dimethylformamide according to a mass ratio of 1:(1.2-1.4):(15-20), and stir at 50-60 ℃ and 200-300 r / min for 10-12 h; remove N,N-dimethylformamide by rotary evaporation; wash the obtained product with anhydrous ethanol for 2-4 times; and vacuum dry at 40-50 ℃ for 10-12 h to prepare modified nanometer cerium dioxide; (2) uniformly mix pre-irradiated polyethylene, vinyl phosphonic acid and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine according to a mass ratio of 1:(0.02-0.04):(0.04-0.06) in a nitrogen atmosphere, and mix in a torque rheometer at 160-180 ℃ and 60-80 rpm for 10-12 min to prepare pre-modified polyethylene; uniformly mix the pre-modified polyethylene, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine and N,N-dimethylformamide according to a mass ratio of 1:(0.1-0.2):(15-20), and stir at 40-60 ℃ and 200-300 r / min for 2-4 h; drop 20 wt% sodium hydroxide aqueous solution at a rate of 5 ml / min and at a speed of 0.2-0.3 times the mass of the pre-modified polyethylene; stir at 80-100 ℃ and 200-300 r / min for 6-8 h; cool to room temperature; filter; remove N,N-dimethylformamide by rotary evaporation; add deionized water in an amount of 20-30 times the mass of the pre-modified polyethylene; stir at room temperature and 300-500 r / min for 10-20 min; filter and wash with deionized water for 2-4 times; and vacuum dry at 60-70 ℃ for 10-12 h to prepare modified polyethylene; (3) uniformly mix the modified polyethylene and the modified nanometer cerium dioxide according to a mass ratio of 1:(0.04-0.06), and melt extrude in a double-screw extruder; injection mold; cool to room temperature; demold and take out to prepare 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 nanometer cerium dioxide in step (1) is as follows: 2-chloroethyl triethoxysilane and 90wt% ethanol aqueous solution are uniformly mixed at a mass ratio of 1: (10-12), ultrasonic dispersion is carried out for 20-40 min, 2-chloroethyl triethoxysilane is added in an amount of 0.1-0.2 times of the mass of the nanometer cerium dioxide, uniform mixing is carried out, ultrasonic dispersion is carried out for 30-40 min, stirring is carried out at 75-80 DEG C and 200-300 r / min for 8-10 h, filtration is carried out, washing is carried out with anhydrous ethanol for 2-4 times, vacuum drying is carried out at 60-70 DEG C for 10-12 h, and the pre-modified nanometer cerium dioxide is prepared.

4. The method for preparing a rare earth modified polymer material according to claim 2, characterized in that, The process parameters of the double-screw extruder in step (3) are as follows: the temperature of the first zone is 180-185 DEG C, the temperature of the second zone is 185-190 DEG C, the temperature of the third zone is 190-195 DEG C, the temperature of the fourth zone is 195-200 DEG C, the temperature of the fifth zone is 200-205 DEG C, and the screw rotation speed is 180-200 r / min.

5. The method for preparing a rare earth modified polymer material according to claim 2, characterized in that, The preparation process of the pre-irradiated polyethylene is as follows: under an air atmosphere, polyethylene is subjected to... 60 Pre-irradiated polyethylene was prepared by irradiating with Co-γ rays at room temperature with an absorbed dose of 25-75 kGy.

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