Antibacterial and antifouling PE composite material and preparation method thereof

Abstract

The application discloses an antibacterial and antifouling PE composite material and a preparation method thereof. The antibacterial and antifouling PE composite material is prepared from the following raw materials in parts by weight: 90 parts of PE, 1-8 parts of antibacterial and antifouling agent Fe3O4-CeO2@XG, 1 part of preservative, 0.5-1 parts of antioxidant 1010 and 1-3 parts of polyethylene wax. The antibacterial and antifouling agent is prepared by taking xanthan gum (XG) with antibacterial and antifouling properties as a carrier, loading Fe-doped cerium oxide Fe3O4-CeO2@XG, combining Fe3O4 with heat resistance and CeO2 with excellent antibacterial properties, and then improving the dispersibility of the antibacterial and antifouling agent in the matrix through the xanthan gum, so that the performance of the antibacterial and antifouling agent can be fully exerted in the matrix. The antibacterial and antifouling agent Fe3O4-CeO2@XG is adopted, the antibacterial and antifouling properties of the PE material can be effectively improved, and the PE composite material with excellent performance is prepared.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of polymer composite processing, and particularly relates to an antibacterial and antifouling PE composite material and a preparation method thereof. BACKGROUND

[0002] Polyethylene (PE) is a thermoplastic resin prepared by polymerization of ethylene, and its yield accounts for about 1 / 4 of the total amount of plastics. PE is widely used in life, such as the production of films, daily necessities, various sizes of hollow containers for industry, packaging calendaring tapes and ligature tapes, ropes, fishing nets and braided fibers, electric wires and cables, etc. Not only because of the excellent chemical properties of PE, such as excellent low-temperature resistance, acid and alkali corrosion resistance, good chemical stability, but also because of its excellent mechanical properties, such as high toughness and strength, high impact strength and good impact resistance. Polyethylene is a linear polymer with a structure similar to that of alkanes, and belongs to a long-chain aliphatic hydrocarbon. Since the -C-C- chain is a flexible chain and is a linear long chain, polyethylene is a thermoplastic polymer with good flexibility. Since the molecules are symmetrical and no polar groups exist, the intermolecular force is relatively small. In order to expand the application range of PE in life, it is necessary to functionalize and modify PE to improve its antibacterial and antifouling properties, so as to better apply it in the fields of packaging and containers. Therefore, the development of antibacterial and antifouling PE plastics has significant social and economic value.

[0003] Cerium oxide is a stable metal particle with good catalytic activity and stability. The variable valence property of CeO2 makes it have good photoelectric performance, and it can be doped in other materials for modification. Cerium oxide particles, especially nanoscale cerium oxide particles, have significant antibacterial properties and wide application prospects in many fields. Four-iron oxide nanoparticles have low surface energy, high specific surface area and good chemical stability, which makes them have wide application potential in the field of hydrophobic antifouling. By controlling the size and morphology of the nanoparticles, materials with different hydrophobic properties can be prepared, and the combination of CeO2 particles can greatly enhance their antibacterial and antifouling ability.

[0004] Xanthan gum (XG) is a non-toxic, high biocompatibility, cost-effective natural gum obtained from renewable resources. The structure of XG is composed of D-glucose, D-mannose and D-glucuronic acid in a ratio of 2:2:1, which has unique rheological properties, good water solubility, stability to heat and acid and alkali, and good compatibility with various salts. It can be widely used in food, petroleum, medicine and other 20 industries. It is the largest production scale and most widely used microbial polysaccharide in the world. Xanthan gum can inhibit the growth of bacteria by reducing the enzyme activity on the cell membrane, and delay the formation of biofilm by reducing the transcription level of genes related to biofilm formation to achieve antibacterial effect. One of the main characteristics of XG is easy modification, which can improve its performance by cross-linking various materials. In particular, polysaccharides modified by nanoparticles have excellent chemical and physical activity.

[0005] Based on this, the present application provides an antibacterial and antifouling PE composite material and a preparation method thereof. SUMMARY

[0006] The purpose of the present application is to provide an antibacterial and antifouling PE composite material and a preparation method thereof. The formula of the present application is scientific and reasonable, and the process flow is simple and practical. By adding an antibacterial and antifouling agent, the produced PE composite material has excellent antibacterial and antifouling properties.

[0007] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0008] An antibacterial and antifouling PE composite material, the PE composite material comprises the following raw materials in terms of weight fraction:

[0009] Polyethylene 90 parts;

[0010] Antibacterial and antifouling agent 1-8 parts;

[0011] Antioxidant 1010 0.5-1 part;

[0012] Polyethylene wax 1-3 parts;

[0013] Preservative sodium benzoate 1 part;

[0014] The antibacterial and antifouling agent is Fe3O4-CeO2@XG.

[0015] The preparation steps of the antibacterial antifouling agent Fe3O4-CeO2@XG are as follows: 1.95 g of FeCl3·6H2O and 4.7 g of FeCl2·4H2O are dissolved in 120 mL of deionized water, Ce(NO3)4·6H2O is added, 1.7 g of xanthan gum is added after dissolution, and stirring is carried out at 75 °C for 80 minutes; 20 mL of 25% mass fraction of ammonium hydroxide is added dropwise to the solution within 25 minutes, the pH of the solution is 12, and the solution is reacted at 80 °C for 95 minutes to obtain Fe3O4-CeO2@XG; Fe3O4-CeO2@XG is separated by keeping an external magnet, washed with deionized water three times, dried at 60 °C for 24 hours, and then ground to obtain Fe3O4-CeO2@XG powder.

[0016] The preparation method of the above antibacterial antifouling PE composite material comprises the following steps:

[0017] (1) The antibacterial antifouling agent, antioxidant 1010, polyethylene wax and preservative sodium benzoate are mixed and then added to a high-speed mixer and mixed with polyethylene, and then dried at 60 °C for 1 h;

[0018] (2) The material obtained in step (1) is added to a double-screw extruder, and the material is extruded and granulated to obtain a master batch;

[0019] (3) The master batch obtained in step (2) is dried, and then injection molding is performed to obtain the antibacterial antifouling PE composite material.

[0020] Further, the rotating speed of the high-speed mixer in step (1) is 300 r / min, and the temperature is 60 °C.

[0021] Further, the extrusion temperature of the double-screw extruder used in step (2) is: the first section is 180 °C, the second section is 175 °C, the third section is 170 °C, the fourth section is 165 °C, and the fifth section is 160 °C; the screw rotating speed is 10 r / min.

[0022] Further, the drying temperature in step (3) is 60 °C, and the drying time is 1 h; during injection molding, the injection molding temperatures from the feeding port to the discharging port are: the first section temperature is 200 °C, the second section temperature is 190 °C, the third section temperature is 180 °C, the fourth section temperature is 170 °C, and the fifth section temperature is 160 °C, the injection molding pressure is 135 MPa, and the holding pressure is 40 MPa.

[0023] The application prepares the antibacterial and antifouling PE composite material by the method of melt blending of the antibacterial and antifouling agent, the antibacterial and antifouling agent takes the xanthan gum (XG) as the carrier, the XG is non-toxic and has good biocompatibility, the dispersibility of the XG in the high molecular polymer resin is very good due to the existence of the hydroxyl, aldehyde and other groups on the molecular chain, and the surface is modified by loading Fe3O4-CeO2, when the Fe3O4-CeO2 has excellent thermal stability, chemical stability and antibacterial and antifouling performance and cooperates with the XG, not only the antibacterial and antifouling performance of the filler is improved, but also the dispersibility of the antibacterial and antifouling agent in the base resin is better than that of the simple inorganic particle, so that the antibacterial performance of the polymer base is further improved. The Fe3O4-CeO2 loaded on the XG can effectively reduce the occurrence of the agglomeration, and can fully play the performance of the antibacterial and antifouling agent. The interaction between the Fe3O4-CeO2 and the XG, the obtained antibacterial and antifouling agent Fe3O4-CeO2@XG has more excellent performance. The obtained modified material is used as the antibacterial and antifouling agent and is melt compounded with the polyethylene base resin, so that the polyethylene composite material with excellent antibacterial and antifouling performance and stability can be prepared.

[0024] The application has the beneficial effects that:

[0025] (1) The antibacterial and antifouling filler obtained by loading the cerium oxide and the magnetite on the xanthan gum can improve the compatibility with the base resin, so that the antibacterial and antifouling filler is more uniformly and effectively dispersed in the base resin, not only the mechanical performance of the composite material is improved, but also the antibacterial and antifouling performance of the composite material is improved through the synergistic effect of the three.

[0026] (2) The two kinds of inorganic particles of the cerium oxide and the magnetite used in the application have excellent thermal stability, the antibacterial and antifouling filler obtained by loading the two kinds of inorganic particles on the xanthan gum with good heat resistance has more excellent thermal stability, on the one hand, the thermal stability of the composite material is improved, and on the other hand, the antibacterial and antifouling performance of the obtained composite material is stably played out in the processing process.

[0027] (3) The inorganic particle and the polysaccharide are combined in the application, the obtained antibacterial and antifouling filler not only has excellent performance, but also has a wider application range, and effectively improves the strength and wear resistance of the polymer. The prepared antibacterial agent has the advantages of inorganic antibacterial agent and organic antibacterial agent, and the addition of the magnetite improves the hydrophobicity, so that the obtained antibacterial and antifouling agent can play a longer role. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 It is the Fourier infrared spectrum of Fe3O4-CeO2@XG.

[0029] Figure 2 It is the SEM diagram of XG.

[0030] Figure 3 SEM image of Fe3O4-CeO2@XG.

[0031] Figure 4 SEM image of the antibacterial and antifouling PE composite material prepared in Example 4 of the application. DETAILED DESCRIPTION

[0032] The application will be further described in conjunction with specific examples, which make the application easier to understand, but the application is not limited to these examples only.

[0033] Example 1

[0034] The preparation method of the antibacterial and antifouling PE composite material is as follows:

[0035] 1. The specific preparation process of the antibacterial and antifouling agent Fe3O4-CeO2@XG:

[0036] Dissolve 1.95 g of FeCl3·6H2O and 0.72 g of FeCl2·4H2O in 120 mL of deionized water, dissolve 4.7 g of Ce(NO3)4·6H2O in the above solution, and then add 1.7 g of XG (Shanghai Maikelin Biotechnology Co., Ltd., batch number C16107847) and stir at 75 ℃ for 80 minutes. Next, add 20 mL of ammonium hydroxide (25% by mass) dropwise to the above solution within 25 minutes to adjust the pH of the solution to 12. Continue the reaction at 80 ℃ for about 95 minutes, and the color of the suspension changes to dark brown, indicating the combination of Fe3O4-CeO2 and XG. Separate Fe3O4-CeO2@XG by maintaining an external magnet, and wash with deionized water three times to remove any unreacted raw materials. Finally, dry the product at 60 ℃ for 24 hours, and then grind to obtain Fe3O4-CeO2@XG powder.

[0037] 1. Dissolve 1.95 g of FeCl3·6H2O and 0.72 g of FeCl2·4H2O in 120 mL of deionized water, dissolve 4.7 g of Ce(NO3)4·6H2O in the above solution, and then add 1.7 g of XG (Shanghai Maikelin Biotechnology Co., Ltd., batch number C16107847) and stir at 75 ℃ for 80 minutes. Next, add 20 mL of ammonium hydroxide (25% by mass) dropwise to the above solution within 25 minutes to adjust the pH of the solution to 12. Continue the reaction at 80 ℃ for about 95 minutes, and the color of the suspension changes to dark brown, indicating the combination of Fe3O4-CeO2 and XG. Separate Fe3O4-CeO2@XG by maintaining an external magnet, and wash with deionized water three times to remove any unreacted raw materials. Finally, dry the product at 60 ℃ for 24 hours, and then grind to obtain Fe3O4-CeO2@XG powder.

[0038] 2. Add 1 part by weight of Fe3O4-CeO2@XG to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, and 1 part by weight of preservative sodium benzoate, mix uniformly, and then mix with 90 parts by weight of PE particles in a high-speed mixer. The rotation speed of the high-speed mixer is 300 r / min, and the temperature is 60 ℃. Then place it in a 60 ℃ oven for drying for 1 hour.

[0039] 3. The above dried raw materials are added into a twin-screw extruder, the first section temperature of the twin-screw extruder is 180℃, the second section temperature is 175℃, the third section temperature is 170℃, the fourth section temperature is 165℃, and the fifth section temperature is 160℃; the rotation speed of the screw is 10r / min; and the mixed master batch is obtained by extrusion granulation.

[0040] 4. The mixed master batch obtained by the twin-screw extruder and the granulator is dried in a 60℃ oven for 1 hour, and injection molding is performed by using an injection molding machine, the temperature of the injection molding machine from the feeding port to the discharging port is as follows: the first section temperature: 200℃, the second section temperature: 190℃, the third section temperature: 180℃, the fourth section temperature: 170℃, and the fifth section temperature: 160℃; the injection pressure: 135MPa; and the holding pressure: 40MPa, so that the antibacterial and antifouling PE composite material is obtained.

[0041] Figure 1 The Fourier infrared spectrum of the antibacterial and antifouling agent Fe3O4-CeO2@XG prepared in the application is shown in the figure. The peak at 480cm -1 corresponds to the anti-symmetric Ce-O-Ce stretching mode of the surface bridged oxide; and the peak at 1074cm -1 corresponds to the Ce-Fe-O and Fe-O-Ce stretching vibration peaks, and the typical peak at 1633cm -1 is the C=O bond on the xanthan gum. The spectrum band at 2926cm -1 is the C-H bond. It can be seen that after the XG and Fe3O4-CeO2 are compounded, the peaks of Ce-Fe-O and Fe-O-Ce are obviously increased on the XG curve, which indicates that the antibacterial and antifouling agent Fe3O4-CeO2@XG is successfully synthesized.

[0042] Figure 2 The SEM image of the XG is shown in the figure. It can be seen that the surface of the XG is uneven, but relatively smooth.

[0043] Figure 3 The SEM image of the Fe3O4-CeO2@XG prepared in the application is shown in the figure. Compared with Figure 2 , the surface of the XG obviously grows small particles, which is the Fe3O4-CeO2 loaded on the surface of the XG.

[0044] Example 2

[0045] The preparation method of the antibacterial and antifouling PE composite material is as follows:

[0046] 1. The preparation process of the antibacterial and antifouling agent Fe3O4-CeO2@XG is the same as that in Example 1.

[0047] 2. 2 parts by weight of Fe3O4-CeO2@XG were added to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, 1 part by weight of preservative sodium benzoate, mixed uniformly, and then mixed with 90 parts by weight of PE particles in a high-speed mixer, the speed of the high-speed mixer was 300 r / min, the temperature was 60°C, and then placed in a 60°C oven for drying for 1 hour.

[0048] 3. The dried raw materials were added to a twin-screw extruder, the first section temperature of the twin-screw extruder was 180°C, the second section temperature was 175°C, the third section temperature was 170°C, the fourth section temperature was 165°C, and the fifth section temperature was 160°C; the screw speed was 10 r / min; and the mixed master batch was obtained by extrusion granulation.

[0049] 4. The mixed master batch obtained by the twin-screw extruder and the granulator was dried in a 60°C oven for 1 hour, and injection molding was performed by an injection molding machine, the temperature of the injection molding machine from the feeding port to the discharge port was first section temperature: 200°C, second section temperature: 190°C, third section temperature: 180°C, fourth section temperature: 170°C, and fifth section temperature: 160°C; the injection pressure was 135 MPa; and the holding pressure was 40 MPa, to obtain the antibacterial and antifouling PE composite material.

[0050] Example 3

[0051] The preparation method of the antibacterial and antifouling PE composite material is as follows:

[0052] 1. The preparation process of the antibacterial and antifouling agent Fe3O4-CeO2@XG was the same as that of Example 1.

[0053] 2. 4 parts by weight of Fe3O4-CeO2@XG were added to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, 1 part by weight of preservative sodium benzoate, mixed uniformly, and then mixed with 90 parts by weight of PE particles in a high-speed mixer, the speed of the high-speed mixer was 300 r / min, the temperature was 60°C, and then placed in a 60°C oven for drying for 1 hour.

[0054] 3. The dried raw materials were added to a twin-screw extruder, the first section temperature of the twin-screw extruder was 180°C, the second section temperature was 175°C, the third section temperature was 170°C, the fourth section temperature was 165°C, and the fifth section temperature was 160°C; the screw speed was 10 r / min; and the mixed master batch was obtained by extrusion granulation.

[0055] 4. The mixed master batch obtained by the twin-screw extruder and the granulator is dried in a 60℃ oven for 1 hour, and injection molding is performed by using an injection molding machine, the temperature of the injection molding machine from the feeding port to the discharging port is respectively: the first section temperature: 200℃, the second section temperature: 190℃, the third section temperature: 180℃, the fourth section temperature: 170℃, the fifth section temperature: 160℃; the injection pressure: 135MPa; the holding pressure: 40MPa, to obtain the antibacterial and antifouling PE composite material.

[0056] Example 4

[0057] The preparation method of the antibacterial and antifouling PE composite material is specifically as follows:

[0058] 1. The preparation process of the antibacterial and antifouling agent Fe3O4-CeO2@XG is the same as that in Example 1.

[0059] 2. 6 parts by weight of Fe3O4-CeO2@XG is added to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, and 1 part of preservative sodium benzoate, and then uniformly mixed, and then uniformly mixed with 90 parts by weight of PE particles in a high-speed mixer, the rotating speed of the high-speed mixer is 300r / min, and the temperature is 60℃, and then placed in a 60℃ oven for drying for 1 hour.

[0060] 3. The dried raw materials are added to a twin-screw extruder, the first section temperature of the twin-screw extruder is 180℃, the second section temperature is 175℃, the third section temperature is 170℃, the fourth section temperature is 165℃, and the fifth section temperature is 160℃; the rotating speed of the screw is 10r / min; and the mixed master batch is obtained by extrusion granulation.

[0061] 4. The mixed master batch obtained by the twin-screw extruder and the granulator is dried in a 60℃ oven for 1 hour, and injection molding is performed by using an injection molding machine, the temperature of the injection molding machine from the feeding port to the discharging port is respectively: the first section temperature: 200℃, the second section temperature: 190℃, the third section temperature: 180℃, the fourth section temperature: 170℃, the fifth section temperature: 160℃; the injection pressure: 135MPa; the holding pressure: 40MPa, to obtain the antibacterial and antifouling PE composite material.

[0062] Figure 4 The SEM diagram of the antibacterial and antifouling PE composite material prepared in Example 4 of the present application can be seen in the figure. It can be seen that the antibacterial and antifouling filler Fe3O4-CeO2@XG is uniformly dispersed in the polyethylene, and has good compatibility with the polyethylene.

[0063] Example 5

[0064] The preparation method of the antibacterial and antifouling PE composite material is specifically as follows:

[0065] 1. The preparation process of the antibacterial and antifouling agent Fe3O4-CeO2@XG is the same as that of Example 1.

[0066] 2. 8 parts by weight of Fe3O4-CeO2@XG were added to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, and 1 part by weight of preservative sodium benzoate, and then mixed uniformly. After that, 90 parts by weight of PE particles were mixed uniformly in a high-speed mixer at a speed of 300 r / min and a temperature of 60°C, and then dried in an oven at 60°C for 1 hour.

[0067] 3. The dried raw materials were added to a twin-screw extruder, and the first, second, third, fourth, and fifth sections of the twin-screw extruder were set to temperatures of 180°C, 175°C, 170°C, 165°C, and 160°C, respectively. The screw speed was 10 r / min. The mixed masterbatch was obtained by extrusion granulation.

[0068] 4. The mixed masterbatch obtained from the twin-screw extruder and the granulator was dried in an oven at 60°C for 1 hour, and then injection molded using an injection molding machine. The temperatures of the injection molding machine from the feeding port to the discharging port were first section: 200°C, second section: 190°C, third section: 180°C, fourth section: 170°C, and fifth section: 160°C. The injection pressure was 135 MPa, and the holding pressure was 40 MPa. The antibacterial and antifouling PE composite material was obtained.

[0069] Comparative Example 1

[0070] 1. 90 parts by weight of PE particles were mixed uniformly with 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, and 1 part by weight of preservative sodium benzoate in a high-speed mixer at a speed of 300 r / min and a temperature of 60°C, and then dried in an oven at 60°C for 1 hour.

[0071] 2. The dried raw materials were added to a twin-screw extruder, and the first, second, third, fourth, and fifth sections of the twin-screw extruder were set to temperatures of 180°C, 175°C, 170°C, 165°C, and 160°C, respectively. The screw speed was 10 r / min. The mixed masterbatch was obtained by extrusion granulation.

[0072] 3. The mixed masterbatch obtained from the twin-screw extruder and the granulator was dried in an oven at 60°C for 1 hour, and then injection molded using an injection molding machine. The temperatures of the injection molding machine from the feeding port to the discharging port were first section: 200°C, second section: 190°C, third section: 180°C, fourth section: 170°C, and fifth section: 160°C. The injection pressure was 135 MPa, and the holding pressure was 40 MPa. The antibacterial and antifouling PE composite material was obtained.

[0073] Comparative Example 2

[0074] 1. Detailed preparation process of antibacterial antifouling agent Fe3O4-CeO2:

[0075] Dissolve 1.95 g FeCl3·6H2O and 0.72 g FeCl2·4H2O in 120 mL deionized water, then add 4.7 g Ce(NO3)4·6H2O, stir at 75 ℃ for 80 minutes. Next, add 20 mL ammonium hydroxide (25%) dropwise to the solution within 25 minutes, adjust the pH of the solution to 12, and continue the reaction at 80 ℃ for about 95 minutes. Then the color of the suspension turns dark brown, Fe3O4-CeO2 is separated by maintaining an external magnet, and washed with deionized water three times to remove any unreacted raw materials. Finally, dry the product at 60 ℃ for 24 hours, then grind to obtain Fe3O4-CeO2 powder.

[0076] 2. Add 6 parts by weight of Fe3O4-CeO2 to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, and 1 part by weight of preservative sodium benzoate, mix uniformly, then mix with 90 parts by weight of PE particles in a high-speed mixer, the speed of the high-speed mixer is 300 r / min, the temperature is 60 ℃, then place in a 60 ℃ oven for drying for 1 hour.

[0077] 3. Add the dried raw materials to a twin-screw extruder, the first segment temperature of the twin-screw extruder is 180 ℃, the second segment temperature is 175 ℃, the third segment temperature is 170 ℃, the fourth segment temperature is 165 ℃, and the fifth segment temperature is 160 ℃; the screw speed is 10 r / min; the mixed masterbatch is obtained by extrusion granulation.

[0078] 4. Dry the mixed masterbatch obtained from the twin-screw extruder and the granulator in a 60 ℃ oven for 1 hour, and injection mold with an injection molding machine, the temperature of the injection molding machine from the feed port to the discharge port is first segment temperature: 200 ℃, second segment temperature: 190 ℃, third segment temperature: 180 ℃, fourth segment temperature: 170 ℃, and fifth segment temperature: 160 ℃; injection pressure: 135 MPa; holding pressure: 40 MPa, to obtain an antibacterial antifouling PE composite material.

[0079] Comparative Example 3

[0080] 1. Add 6 parts by weight of XG to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax, and 1 part by weight of preservative sodium benzoate, mix uniformly, then mix with 90 parts by weight of PE particles in a high-speed mixer, the speed of the high-speed mixer is 300 r / min, the temperature is 60 ℃, then place in a 60 ℃ oven for drying for 1 hour.

[0081] 2. The dried raw material is added to a twin-screw extruder. The temperature of the first section of the twin-screw extruder is 180℃, the second section is 175℃, the third section is 170℃, the fourth section is 165℃, and the fifth section is 160℃. The screw speed is 10 r / min. Mixed masterbatch is obtained by extrusion granulation.

[0082] 3. The mixed masterbatch obtained from the twin-screw extruder and granulator is dried in a 60℃ oven for 1 hour, and then injection molded using an injection molding machine. The temperatures of the injection molding machine from the inlet to the outlet are as follows: first stage temperature: 200℃, second stage temperature: 190℃, third stage temperature: 180℃, fourth stage temperature: 170℃, and fifth stage temperature: 160℃; injection pressure: 135MPa; holding pressure: 40MPa, to obtain an antibacterial and stain-resistant PE composite material.

[0083] Comparative Example 4

[0084] 1. Specific preparation process of antibacterial and antifouling agent Fe3O4-CeO2:

[0085] Dissolve 1.95 g FeCl3·6H2O and 0.72 g FeCl2·4H2O in 120 mL of deionized water, then add 4.7 g...

[0086] Ce(NO3)4·6H2O was stirred at 75 °C for 80 minutes. Next, 20 mL of ammonium hydroxide (25% by mass) was added dropwise to the solution over 25 minutes to adjust the pH to 12. The reaction was continued at 80 °C for approximately 95 minutes. Subsequently, the suspension turned dark brown. Fe3O4-CeO2 was separated by maintaining an external magnet and washed three times with deionized water to remove any unreacted raw materials. Finally, the product was dried at 60 °C for 24 hours and then ground to obtain Fe3O4-CeO2 powder.

[0087] 2. Add 3 parts by weight of XG and 3 parts by weight of Fe3O4-CeO2 to 0.5 parts by weight of antioxidant 1010, 1 part by weight of polyethylene wax and 1 part by weight of preservative sodium benzoate. Mix evenly, then mix evenly with 90 parts by weight of PE granules in a high-speed mixer at a speed of 300 r / min and a temperature of 60℃. Then place in a 60℃ oven to dry for 1 hour.

[0088] 3. Add the dried raw material to a twin-screw extruder. The temperature of the first section of the twin-screw extruder is 180℃, the second section is 175℃, the third section is 170℃, the fourth section is 165℃, and the fifth section is 160℃. The screw speed is 10 r / min. The mixed masterbatch is obtained by extrusion granulation.

[0089] 4. The mixed master batch obtained by the twin-screw extruder and the granulator is dried in an oven at 60℃ for 1 hour, and injection molding is performed by an injection molding machine, the temperature of the injection molding machine from the feeding port to the discharging port is as follows: the first section temperature: 200℃, the second section temperature: 190℃, the third section temperature: 180℃, the fourth section temperature: 170℃, and the fifth section temperature: 160℃; the injection pressure: 135MPa; the holding pressure: 40MPa, to obtain the antibacterial and antifouling PE composite material.

[0090] Table 1 is the performance test results of each example and each comparative example.

[0091]

[0092] Table 1 is the performance test results of each example and each comparative example. From the above performance test results, it can be clearly seen that in Examples 1-5, with the increase of the amount of antibacterial and antifouling filler, the tensile strength of the PE composite material shows a trend of first increasing and then slightly decreasing, but the antibacterial and antifouling properties are continuously improved. When the amount of antibacterial and antifouling agent reaches 8 parts (Example 5), the mechanical properties are slightly lower than those of Example 4, which may be due to the agglomeration of the antibacterial and antifouling agent in the matrix material, resulting in a decrease in mechanical properties and antibacterial properties, but the antifouling performance is still slightly improved. In terms of comprehensive performance, the best effect is obtained when the amount of antibacterial and antifouling agent Fe3O4-CeO2@XG is 6 parts by weight. As can be seen from the comparison of Comparative Example 1, Comparative Example 2 and Example 4, although the compatibility of Fe3O4-CeO2 with the matrix is general, due to its excellent performance, it can still improve the mechanical properties and antibacterial properties of the PE composite material to a certain extent, but the improvement of the antifouling performance is smaller. As can be seen from the comparison of Comparative Example 1, Comparative Example 3 and Example 4, XG has good compatibility with the matrix, and the mechanical properties are also greatly improved, and the antibacterial properties and antifouling properties of the PE composite material are also greatly improved, which is a manifestation of the good performance of XG. As can be seen from Comparative Examples 1-4, when Fe3O4-CeO2+XG is used as the antibacterial and antifouling agent, XG can improve the compatibility of Fe3O4-CeO2 with the matrix resin to a certain extent, so that the mechanical properties of the PE composite material are better than those of Comparative Example 2, and the antibacterial and antifouling properties are higher than those of Comparative Examples 2 and 3.

[0093] The above description is only the preferred embodiment of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application shall be included in the scope of the present application.

Claims

1. An antibacterial and antifouling PE composite material, characterized in that: The PE composite material comprises the following raw materials by weight fraction: 90 parts of polyethylene; 1-8 parts antibacterial and antifouling agent; Antioxidant 1010: 0.5-1 part; 1-3 parts of polyethylene wax; Sodium benzoate preservative 1 part; The antibacterial and antifouling agent is Fe3O4-CeO2@XG; The preparation steps of the antibacterial and antifouling agent Fe3O4-CeO2@XG are as follows: 1.95 g FeCl3·6H2O and FeCl2·4H2O are dissolved in 120 mL of deionized water, 4.7 g Ce(NO3)4·6H2O is added, and after dissolution, 1.7 g xanthan gum is added. After stirring at 75 °C for 80 minutes, 25% ammonium hydroxide is added dropwise to adjust the pH of the solution to 12. The reaction is carried out at 80 °C for 95 minutes to obtain Fe3O4-CeO2@XG. Fe3O4-CeO2@XG is separated by maintaining an external magnet, washed three times with deionized water, dried at 60 °C for 24 hours, and then ground to obtain Fe3O4-CeO2@XG powder.

2. A method for preparing the antibacterial and antifouling PE composite material as described in claim 1, characterized in that: Includes the following steps: (1) Mix the antibacterial and antifouling agent, antioxidant 1010, polyethylene wax and preservative evenly, add them to a high-speed mixer and mix evenly with polyethylene, then dry at 60°C for 1 hour; (2) Add the material obtained in step (1) into a twin-screw extruder and granulate it to obtain masterbatch; (3) Dry the masterbatch obtained in step (2) and then perform injection molding to obtain antibacterial and antifouling PE composite material.

3. The preparation method according to claim 2, characterized in that: The high-speed mixer mentioned in step (1) has a rotation speed of 300 r / min and a temperature of 60℃.

4. The preparation method according to claim 2, characterized in that: The extrusion temperatures of the twin-screw extruder used in step (2) are: 180℃ for the first section, 175℃ for the second section, 170℃ for the third section, 165℃ for the fourth section, and 160℃ for the fifth section; the screw speed is 10 r / min.

5. The preparation method according to claim 2, characterized in that: The drying temperature in step (3) is 60°C and the time is 1 hour; during injection molding, the injection temperatures from the inlet to the outlet are respectively: first stage temperature: 200°C, second stage temperature: 190°C, third stage temperature: 180°C, fourth stage temperature: 170°C, fifth stage temperature: 160°C, injection pressure is 135MPa, and holding pressure is 40MPa.

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