Antibacterial PE composite material and preparation method thereof

Abstract

The application discloses an antibacterial PE composite material and a preparation method thereof, and belongs to the field of high polymer composite materials. The antibacterial PE composite material is prepared from the following raw materials in parts by weight: 90 parts of PE, 1-6 parts of an antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP, 1.5-2.5 parts of glycerol, 1-2 parts of an antioxidant 1010 and 1-3 parts of polyethylene wax. The antibacterial agent is prepared by using modified hydroxyapatite as a carrier and loading manganese-doped cerium oxide; the Mn-CeO2 obtained by using Mn-doped CeO2 and HAP modified by PDA and HDTBP can simultaneously improve the antibacterial performance of the antibacterial agent and the dispersibility and compatibility of the antibacterial agent in a matrix, so that the performance of the antibacterial agent can be fully exerted in the matrix. The Mn-CeO2 / HAP@PDA-HDTBP is used as the antibacterial agent, the antibacterial performance and the mechanical performance of the PE 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 high polymer composite materials, and particularly relates to an antibacterial PE composite material and a preparation method thereof. BACKGROUND

[0002] Polyethylene (PE) is a thermoplastic resin prepared by polymerization of ethylene, and the yield thereof accounts for about 1 / 4 of the total amount of plastics. PE has excellent low-temperature resistance (the minimum use temperature can reach -100 to -70 DEG C), and the heat resistance is not high, which is improved with the increase of relative molecular mass and crystallinity. PE has good chemical stability and can resist the corrosion of most acids and bases. PE is widely used in the production of films, daily necessities, various sizes of hollow containers for industry, pipe materials, calendaring tapes and ligature tapes for packaging, ropes, fishing nets and braided fibers, electric wires and cables, etc. However, the mechanical properties of PE are general, the impact resistance is good, the tensile strength is low, and the anti-cracking property is not good. 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. The wide application of PE in life improves the antibacterial properties, which is a key problem concerning thousands of households.

[0003] Therefore, the development of antibacterial PE plastics has significant social and economic value. SUMMARY

[0004] The application aims to provide an antibacterial PE composite material and a preparation method thereof. The application has scientific and reasonable formula, simple and practical process flow, and the produced PE composite material has excellent mechanical properties and antibacterial properties through the addition of an antibacterial agent.

[0005] To achieve the above-mentioned purpose, the application adopts the following technical scheme:

[0006] An antibacterial PE composite material, according to weight parts, the antibacterial PE composite material comprises PE 90 parts, an antibacterial agent 1-6 parts, glycerol 1.5-2.5 parts, an antioxidant 1-2 parts, and polyethylene wax 1-3 parts, and the antibacterial agent is Mn-CeO2 / HAP@PDA-HDTBP.

[0007] The specific preparation process of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is as follows:

[0008] (1) Preparation of HAP: 5.6 g of Ca(NO3)2·4H2O was added to 300 mL of anhydrous ethanol, and stirred magnetically at 60°C until uniform, then 1.7 g of phosphorus pentoxide (P2O5) was slowly added, and stirring was continued until a sol was formed, and gelled at room temperature. The formed gel was dried at 80°C for 24 hours, then calcined at 700°C for 3 hours to obtain HAP;

[0009] (2) Preparation of HAP@PDA-HDTBP: 1 g of HAP and 2 g of dopamine hydrochloride were added to 400 mL of Tris buffer (PH=8.5), then 100 mL of anhydrous ethanol was added, and after ultrasonic treatment for 1 h, HAP@PDA was obtained by filtration and drying, and then 2 g of dried HAP@PDA and 1 g of hexadecyl tributyl phosphonium bromide (HDTBP) were added to 200 mL of an ethanol-water solution (concentration 95%), and after ultrasonic treatment for 1 h, stirring was carried out at 80°C for 6 h. After the reaction was completed, the product was filtered and washed with ethanol and deionized water several times, and vacuum dried at 60°C for 24 h to obtain HAP@PDA-HDTBP;

[0010] (3) Preparation of Mn-CeO2 / HAP@PDA-HDTBP: 125 mL of NaOH aqueous solution (1.33 mol / L) was gradually added to 125 mL of Mn(CH3COO)2·2H2O aqueous solution (0.44 mol / L) under continuous stirring, then 1.76 g of Ce(NO3)3·6H2O and 8.9 g of HAP@PDA-HDTBP were added, and then the obtained suspension was transferred into a hydrothermal reactor for hydrothermal reaction. After the reaction was completed and cooled to room temperature, the product was washed with deionized water and ethanol several times, and vacuum dried at 60°C for 4 hours to obtain Mn-CeO2 / HAP@PDA-HDTBP.

[0011] Further, in step (1), the mass ratio of phosphorus pentoxide and Ca(NO3)2·4H2O is 1:3.3.

[0012] Further, in step (3), the temperature of the hydrothermal reaction is 100°C, and the time is 10 hours.

[0013] The application also provides a method for preparing the above-mentioned antibacterial PE composite material, comprising the following steps:

[0014] (1) The antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is mixed with glycerol, antioxidant 1010, and polyethylene wax, and then added into a high-speed mixer and mixed uniformly with PE, and then dried at 60°C for 1 h;

[0015] (2) the material dried in step (1) is added into a double screw extruder, and granulation by extrusion is carried out to obtain a master batch;

[0016] (3) the master batch obtained in step (2) is dried in a vacuum drying box for 1 h, and then injection molding is carried out, to obtain an antibacterial PE composite material.

[0017] Further, in step (1), the rotating speed of the high-speed stirrer is 300 r / min, and the temperature is 60 DEG C.

[0018] Further, in step (2), the first section temperature of the double screw extruder is 220 DEG C, the second section temperature is 215 DEG C, the third section temperature is 210 DEG C, the fourth section temperature is 205 DEG C, and the fifth section temperature is 200 DEG C; the rotating speed of the screw is 10 r / min; and the mixed master batch is obtained by extrusion granulation.

[0019] Further, in step (3), injection molding is carried out by using an injection molding machine, and the temperature of the injection molding machine from the feeding port to the discharging port is as follows: the first section temperature is 250 DEG C, the second section temperature is 240 DEG C, the third section temperature is 230 DEG C, the fourth section temperature is 220 DEG C, and the fifth section temperature is 210 DEG C; the injection pressure is 135 MPa; and the holding pressure is 40 MPa, to obtain the antibacterial PE composite material.

[0020] The present application has the following beneficial effects:

[0021] (1) The cerium oxide used in the present application is a stable metal particle, and has good catalytic activity and stability. The cerium ion has excellent antibacterial performance, excellent adsorption performance can adsorb bacteria, improve the antibacterial efficiency, and has high thermal stability and chemical stability, and the structure is not easy to be damaged. The variable valence characteristics of CeO2 make it have good photoelectric performance, and it can be doped in other materials for modification. The cerium oxide particle, especially the nanometer cerium oxide particle, has remarkable antibacterial performance. Mn is combined with CeO2 particles in the form of ion doping as Mn-CeO2, which can further improve the antibacterial efficiency.

[0022] (2) Hydroxyapatite (HAP) is a component of biological bone, and has good adsorption, biocompatibility and bioactivity, and can be effectively dispersed in a high molecular polymer resin. The calcium ion in the hydroxyapatite is relatively large, the linking bond in the compound is relatively weak, and the replacement with other ions can be easily carried out, the cerium salt and manganese salt dissolved in deionized water can be exchanged with the calcium ion in the hydroxyapatite by a hydrothermal method, the Mn and cerium ions are doped into the hydroxyapatite, and the characteristics of Ce and Mn are also added.

[0023] (3) The antibacterial agent of the present application uses non-toxic hydroxyapatite (HAP) as a carrier, and the HAP modified by dopamine and hexadecyl tributyl phosphonium bromide can be well dispersed in the high molecular polymer resin and has certain antibacterial performance, and can improve the mechanical properties of the high molecular resin to a certain extent. The antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is obtained by loading manganese-doped cerium oxide (Mn-CeO2) on the surface of HAP. Because Mn-CeO2 has excellent thermal stability, chemical stability and antibacterial performance, the stability of the antibacterial agent as a whole can be improved, and the dispersibility of the antibacterial agent in the base resin is improved, thereby further improving the antibacterial performance of the polymer base. At the same time, when Mn-CeO2 is loaded on HAP@PDA-HDTBP, the occurrence of agglomeration can be effectively reduced, and the antibacterial performance of the antibacterial agent can be fully utilized, so that the obtained antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP has more excellent performance. The modified material obtained is used as an antibacterial agent in a polymer base, and an antibacterial material with excellent antibacterial performance and stable existence can be prepared.

[0024] (4) The antibacterial PE composite material prepared by the present application has a scientific and reasonable formula and a simple and practical process flow. The antibacterial agent is prepared into an antibacterial PE composite material by a melt blending method. The antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP uses HAP@PDA-HDTBP with excellent biocompatibility as a carrier, and Mn-CeO2 is loaded on the carrier. Because HAP is difficult to modify, PDA is used to increase the active sites, and then HDTBP is used for modification, so that the obtained HAP@PDA-HDTBP can be effectively dispersed in the high molecular polymer resin. Therefore, when Mn-CeO2 with good antibacterial performance is loaded on the surface of HAP@PDA-HDTBP, the antibacterial agent can be more uniformly and effectively dispersed in the base resin under the action of HAP@PDA-HDTBP. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The Fourier infrared spectrum of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP prepared by the present application.

[0026] Figure 2 The SEM image of HAP prepared in Example 1.

[0027] Figure 3 The SEM image of Mn-CeO2 / HAP@PDA-HDTBP prepared in Example 1.

[0028] Figure 4 The SEM image of the antibacterial PE composite material prepared in Example 5 of the present application. DETAILED DESCRIPTION

[0029] The application will be further described with reference to the following specific examples, which are intended to be illustrative only and not limiting.

[0030] Example 1

[0031] The preparation method of the antibacterial PE composite material is as follows:

[0032] 1. The specific preparation process of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is as follows:

[0033] 1) Preparation of HAP: 5.6 g of Ca(NO3)2·4H2O was added to 300 mL of anhydrous ethanol and stirred magnetically at 60°C until uniform, then 1.7 g of phosphorus pentoxide (P2O5) was slowly added, and stirring was continued until a sol was formed, and the gel was gelled at room temperature. The formed gel was dried at 80°C for 24 hours, and then calcined at 700°C for 3 hours to obtain HAP;

[0034] 2) Preparation of HAP@PDA-HDTBP: 1 g of HAP and 2 g of dopamine hydrochloride were added to 400 mL of Tris buffer (PH=8.5), and 100 mL of anhydrous ethanol was added, and after ultrasonic treatment for 1 h, HAP@PDA was obtained by suction filtration and drying. Then 2 g of dried HAP@PDA and 1 g of hexadecyl tributyl phosphonium bromide (HDTBP) were added to 200 mL of ethanol solution (95%), and after ultrasonic treatment for 1 h, stirring was carried out at 80°C for 6 h. After the reaction was completed, filtration was carried out, and ethanol and deionized water were used for washing several times, and vacuum drying was carried out at 60°C for 24 h to obtain HAP@PDA-HDTBP;

[0035] 3) Preparation of Mn-CeO2 / HAP@PDA-HDTBP: 125 mL of NaOH aqueous solution (1.33 mol / L) was gradually added to 125 mL of Mn(CH3COO)2·2H2O aqueous solution (0.44 mol / L) under continuous stirring. In the above solution, 1.76 g of Ce(NO3)3·6H2O and 8.9 g of HAP@PDA-HDTBP were added, and then the obtained suspension was transferred into a hydrothermal reactor and heated at 100°C for 10 hours. After cooling to room temperature, the product was washed with deionized water and ethanol several times, and vacuum drying was carried out at 60°C for 4 hours to obtain Mn-CeO2 / HAP@PDA-HDTBP.

[0036] 2. 1 part by weight of Mn-CeO2 / HAP@PDA-HDTBP is added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010, 1 part by weight of polyethylene wax, and mixed uniformly, and then mixed 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, the temperature is 60℃, and then placed in a 60℃ oven for drying for 1 hour.

[0037] 3. The dried raw materials are added to a twin-screw extruder, the first section temperature of the twin-screw extruder is 220℃, the second section temperature is 215℃, the third section temperature is 210℃, the fourth section temperature is 205℃, and the fifth section temperature is 200℃; the rotation speed of the screw is 10 r / min; and the mixed master batch is obtained by extrusion granulation.

[0038] 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 an injection molding machine, the temperature from the feeding port to the discharging port of the injection molding machine is first section temperature: 250℃, second section temperature: 240℃, third section temperature: 230℃, fourth section temperature: 220℃, and fifth section temperature: 210℃; the injection pressure is 135 MPa; and the holding pressure is 40 MPa, to obtain the antibacterial PE composite material.

[0039] Figure 1 The Fourier infrared spectrum of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP prepared in the present application. The infrared spectrum shows absorption peaks at 570 cm -1 and 607 cm -1 , which correspond to the bending vibration of P-O bond, the peaks in the range of 1035-1096 cm -1 represent the strong stretching vibration of -PO4 group; and the peaks at 1633 cm -1 and 3572 cm -1 are the hydrogen-oxygen stretching vibration peaks in hydroxyapatite. After PDA modification, a weak characteristic peak appears at 1598 cm -1 , which corresponds to the C=C stretching vibration absorption peak in the aromatic ring of PDA, indicating that HAP is modified by PDA. The characteristic peak of -CH3 is found at 2930 cm -1 , which is the characteristic group of HDTBP. This indicates that HAP@PDA-HDTBP is successfully prepared, and then combined with Mn-CeO2 to obtain the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP.

[0040] Figure 2 The SEM image of HAP prepared in Example 1. As can be seen from the figure, the surface of the prepared HAP is relatively smooth.

[0041] Figure 3SEM image of Mn-CeO2 / HAP@PDA-HDTBP prepared for Example 1. As can be seen from the figure, the antibacterial agent Mn-CeO2 is loaded on the surface of the modified HAP with large and rough particles, which proves that the composite antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is successfully prepared.

[0042] Example 2

[0043] The preparation method of the antibacterial PE composite material is specifically as follows:

[0044] 1. The specific preparation process of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is the same as that of Example 1.

[0045] 2. 2 parts by weight of Mn-CeO2 / HAP@PDA-HDTBP were added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010 and 1 part by weight of polyethylene wax, and then mixed uniformly in a high-speed mixer. The rotation speed of the high-speed mixer was 300 r / min, and the temperature was 60℃. Then, the mixture was placed in a 60℃ oven for drying for 1 hour.

[0046] 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 220℃, 215℃, 210℃, 205℃ and 200℃ respectively. The rotation speed of the screw was 10 r / min. The mixed master batch was obtained by extrusion granulation.

[0047] 4. The mixed master batch obtained by the twin-screw extruder and the granulator was dried in a 60℃ oven for 1 hour, and then injection molded by an injection molding machine. The temperatures from the feeding port to the discharging port of the injection molding machine were first section: 250℃, second section: 240℃, third section: 230℃, fourth section: 220℃ and fifth section: 210℃. The injection pressure was 135 MPa, and the holding pressure was 40 MPa. The antibacterial PE composite material was obtained.

[0048] Example 3

[0049] The preparation method of the antibacterial PE composite material is specifically as follows:

[0050] 1. The specific preparation process of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is the same as that of Example 1.

[0051] 2. 3 parts by weight of Mn-CeO2 / HAP@PDA-HDTBP were added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010, 1 part by weight of polyethylene wax, 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.

[0052] 3. The dried raw materials were added to a twin-screw extruder, the first section temperature of the twin-screw extruder was 220°C, the second section temperature was 215°C, the third section temperature was 210°C, the fourth section temperature was 205°C, and the fifth section temperature was 200°C; the screw speed was 10 r / min; and the mixed master batch was obtained by extrusion granulation.

[0053] 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 discharging port was first section temperature: 250°C, second section temperature: 240°C, third section temperature: 230°C, fourth section temperature: 220°C, and fifth section temperature: 210°C; the injection pressure was 135 MPa; and the holding pressure was 40 MPa, to obtain an antibacterial PE composite material.

[0054] Example 4

[0055] The preparation method of the antibacterial PE composite material includes the following steps:

[0056] The preparation method of the antibacterial PE composite material includes the following steps:

[0057] 1. The specific preparation process of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP was the same as that in Example 1.

[0058] 2. 3 parts by weight of Mn-CeO2 / HAP@PDA-HDTBP were added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010, 1 part by weight of polyethylene wax, 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.

[0059] 3. The dried raw materials were added to a twin-screw extruder, the first section temperature of the twin-screw extruder was 220°C, the second section temperature was 215°C, the third section temperature was 210°C, the fourth section temperature was 205°C, and the fifth section temperature was 200°C; the screw speed was 10 r / min; and the mixed master batch was obtained by extrusion granulation.

[0060] 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 using an injection molding machine, the temperature of the injection molding machine from the feeding port to the discharging port is first segment temperature: 250℃, second segment temperature: 240℃, third segment temperature: 230℃, fourth segment temperature: 220℃, and fifth segment temperature: 210℃; the injection pressure is 135MPa; and the holding pressure is 40MPa, to obtain the antibacterial PE composite material.

[0061] Example 5

[0062] The preparation method of the antibacterial PE composite material includes the following specific steps:

[0063] 1. The specific preparation process of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is the same as that in Example 1.

[0064] 2. 5 parts by weight of Mn-CeO2 / HAP@PDA-HDTBP is added into 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010 and 1 part by weight of polyethylene wax, 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 the mixture is placed in a 60℃ oven for drying for 1 hour.

[0065] 3. The dried raw materials are added into a twin-screw extruder, the first segment temperature of the twin-screw extruder is 220℃, the second segment temperature is 215℃, the third segment temperature is 210℃, the fourth segment temperature is 205℃, and the fifth segment temperature is 200℃; the rotating speed of the screw is 10r / min; and the mixed master batch is obtained by extrusion granulation.

[0066] 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 using an injection molding machine, the temperature of the injection molding machine from the feeding port to the discharging port is first segment temperature: 250℃, second segment temperature: 240℃, third segment temperature: 230℃, fourth segment temperature: 220℃, and fifth segment temperature: 210℃; the injection pressure is 135MPa; and the holding pressure is 40MPa, to obtain the antibacterial PE composite material.

[0067] Figure 4 The SEM diagram of the antibacterial PE composite material prepared in Example 5 is shown in the figure, and the compatibility of the antibacterial filler with the polyethylene matrix is obviously good, and the dispersion degree of the filler in the PE is also good.

[0068] Example 6

[0069] The preparation method of the antibacterial PE composite material includes the following specific steps:

[0070] 1. The specific preparation process of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is the same as that in Example 1.

[0071] 2. 6 parts by weight of Mn-CeO2 / HAP@PDA-HDTBP were added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010, and 1 part by weight of polyethylene wax, which were uniformly mixed, and then uniformly mixed with 90 parts by weight of PE particles 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.

[0072] 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 220°C, 215°C, 210°C, 205°C, and 200°C, respectively; the screw speed was 10 r / min; and the mixed masterbatch was obtained by extrusion granulation.

[0073] 4. The mixed masterbatch obtained by the twin-screw extruder and the granulator was dried in an oven at 60°C for 1 hour, and injection molding was performed using an injection molding machine, and the temperatures of the injection molding machine from the feeding port to the discharging port were first, second, third, fourth, and fifth section temperatures of 250°C, 240°C, 230°C, 220°C, and 210°C, respectively; the injection pressure was 135 MPa; and the holding pressure was 40 MPa, to obtain an antibacterial PE composite material.

[0074] Comparative Example 1

[0075] 1. Preparation of HAP: 5.6 g of Ca(NO3)2·4H2O was added to 300 mL of anhydrous ethanol and magnetically stirred at 60°C until uniform, and then 1.7 g of phosphorus pentoxide (P2O5) was slowly added, and stirring was continued until a sol was formed, and the sol was gelled at room temperature. The formed gel was dried at 80°C for 24 hours, and then calcined at 700°C for 3 hours to obtain HAP.

[0076] 2. Preparation of HAP@PDA-HDTBP: 1 g of HAP and 2 g of dopamine hydrochloride were added to 400 mL of Tris buffer (PH=8.5), and then 100 mL of anhydrous ethanol was added, and after ultrasonic treatment for 1 h, HAP@PDA was obtained by suction filtration and drying, and then 2 g of dried HAP@PDA and 1 g of hexadecyl tributyl phosphonium bromide (HDTBP) were added to 200 mL of an ethanol solution (95%), and after ultrasonic treatment for 1 h, stirring was performed at 80°C for 6 h. After the reaction was completed, filtration was performed, and the product was washed with ethanol and deionized water several times, and then dried in a vacuum oven at 60°C for 24 h to obtain HAP@PDA-HDTBP.

[0077] 3. 5 parts by weight of HAP@PDA-HDTBP were added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010, 1 part by weight of polyethylene wax, 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.

[0078] 4. The dried raw materials were added to a twin-screw extruder, the first section temperature of the twin-screw extruder was 220°C, the second section temperature was 215°C, the third section temperature was 210°C, the fourth section temperature was 205°C, and the fifth section temperature was 200°C; the screw speed was 10 r / min; and the mixed master batch was obtained by extrusion granulation.

[0079] 5. 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 discharging port was first section temperature: 250°C, second section temperature: 240°C, third section temperature: 230°C, fourth section temperature: 220°C, and fifth section temperature: 210°C; the injection pressure was 135 MPa; and the holding pressure was 40 MPa, to obtain an antibacterial PE composite material.

[0080] Comparative Example 2

[0081] 1. Preparation of Mn-CeO2: 125 mL of NaOH aqueous solution (1.33 mol / L) was gradually added to 125 mL of Mn(CH3COO)2·2H2O aqueous solution (0.44 mol / L) under continuous stirring. In the above solution, 1.76 g of Ce(NO3)3·6H2O was added, and then the obtained suspension was transferred to a hydrothermal reactor and heated at 100°C for 10 hours. After the reaction was completed, it was cooled to room temperature, centrifuged, and the product was washed several times with deionized water and ethanol, and vacuum dried at 60°C for 4 hours to obtain Mn-CeO2.

[0082] 2. 5 parts by weight of Mn-CeO2 were added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010, 1 part by weight of polyethylene wax, 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.

[0083] 3. The dried raw materials were added to a twin-screw extruder, the first section temperature of the twin-screw extruder was 220°C, the second section temperature was 215°C, the third section temperature was 210°C, the fourth section temperature was 205°C, and the fifth section temperature was 200°C; the screw speed was 10 r / min; and the mixed master batch was obtained by extrusion granulation.

[0084] 4. The mixed master batch obtained from the twin-screw extruder and the granulator is dried in an oven at 60°C for 1 hour, and injection molded by an injection molding machine with the temperature from the feeding port to the discharging port being first segment temperature: 250°C, second segment temperature: 240°C, third segment temperature: 230°C, fourth segment temperature: 220°C, and fifth segment temperature: 210°C; injection pressure: 135 MPa; and holding pressure: 40 MPa, to obtain the antibacterial PE composite material.

[0085] Comparative Example 3

[0086] 1. Preparation of HAP@PDA-HDTBP:

[0087] 1) 5.6 g of Ca(NO3)2·4H2O was added to 300 mL of anhydrous ethanol and magnetically stirred at 60°C until uniform, then 1.7 g of P2O5 was slowly added, and the stirring was continued until a sol was formed, and the gel was kept at room temperature until it gelled. The formed gel was dried at 80°C for 24 hours, and then calcined at 700°C for 3 hours to obtain HAP.

[0088] 2) 1 g of HAP and 2 g of dopamine hydrochloride were added to 400 mL of Tris buffer (PH=8.5), and then 100 mL of anhydrous ethanol was added, and after ultrasonic treatment for 1 h, HAP@PDA was obtained by suction filtration and drying, and then 2 g of dried HAP@PDA and 1 g of hexadecyl tributyl phosphonium bromide (HDTBP) were added to 200 mL of ethanol solution (95%), and after ultrasonic treatment for 1 h, stirring was carried out at 80°C for 6 h. After the reaction was completed, filtration was carried out, and washing was carried out with ethanol and deionized water for several times, and vacuum drying was carried out at 60°C for 24 h to obtain HAP@PDA-HDTBP.

[0089] 2. Preparation of Mn-CeO2: 125 mL of NaOH aqueous solution (1.33 mol / L) was gradually added to 125 mL of Mn(CH3COO)2·2H2O aqueous solution (0.44 mol / L) under continuous stirring. In the above solution, 1.76 g of Ce(NO3)3·6H2O was added, and then the suspension was transferred to a hydrothermal reactor and heated at 100°C for 10 hours. After cooling to room temperature, the product was washed with deionized water and ethanol for several times, and after centrifugation, vacuum drying was carried out at 60°C for 4 hours to obtain Mn-CeO2.

[0090] 3. 4 parts by weight of HAP@PDA-HDTBP and 1 part by weight of Mn-CeO2 were added to 2 parts by weight of glycerol, 1 part by weight of antioxidant 1010, and 1 part by weight of polyethylene wax, and after mixing uniformly, 90 parts by weight of PE particles were mixed uniformly in a high-speed mixer with a rotation speed of 300 r / min and a temperature of 60°C, and then placed in a 60°C oven for drying for 1 hour.

[0091] 4. The dried raw materials are added to a twin-screw extruder, the first section temperature of the twin-screw extruder is 220℃, the second section temperature is 215℃, the third section temperature is 210℃, the fourth section temperature is 205℃, and the fifth section temperature is 200℃; the rotation speed of the screw is 10r / min; and the mixed masterbatch is obtained by extrusion granulation.

[0092] 5. The mixed masterbatch 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 first section temperature: 250℃, second section temperature: 240℃, third section temperature: 230℃, fourth section temperature: 220℃, and fifth section temperature: 210℃; the injection pressure is 135MPa; and the holding pressure is 40MPa, to obtain an antibacterial PE composite material.

[0093] The materials obtained in the examples and the comparative examples are subjected to performance testing, and the results are shown in Table 1.

[0094] Table 1 Performance test results

[0095]

[0096] Table 1 is the performance test results of each example and each comparative example. It can be clearly seen from the above performance test results that, in Examples 1-6, with the increase of the amount of antibacterial agent, the tensile strength of the PE composite material shows a trend of first increasing and then slightly decreasing, and the antibacterial performance also shows a trend of first increasing and then slightly decreasing. When the amount of antibacterial agent reaches 6 parts, the mechanical properties decrease more, which may be due to the agglomeration of the antibacterial agent in the matrix material, resulting in a decrease in mechanical properties. In terms of comprehensive performance, the best effect is obtained when the amount of antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is 5 parts by weight (Example 5). It can be seen from the comparison between Comparative Example 2 and Example 5 that the compatibility of Mn-CeO2 with the matrix is general, and the effect of the composite antibacterial agent is better than that of Mn-CeO2. It can be seen from the comparison between Comparative Example 1 and Example 5 that HAP@PDA-HDTBP has good compatibility with the matrix, and can improve the mechanical properties of the composite material. It can be seen from the comparison between Comparative Examples 1, 2 and Example 5 that, in Example 5, Mn-CeO2 / HAP@PDA-HDTBP is used as the antibacterial agent, and HAP@PDA-HDTBP can improve the compatibility of Mn-CeO2 with the matrix to a certain extent, so that the mechanical properties and antibacterial properties of the PE composite material are better than those of Comparative Examples 1 and 2.

[0097] Those skilled in the art will readily understand that the above description is only preferred examples of the present application and is not intended to limit the present application, and any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An antibacterial PE composite material, characterized by: The antibacterial PE composite material comprises, by weight fraction, 90 parts of PE, 1-6 parts of antibacterial agent, 1.5-2.5 parts of glycerol, 1-2 parts of antioxidant 1010, and 1-3 parts of polyethylene wax; the antibacterial agent is Mn-CeO2 / HAP@PDA-HDTBP; The preparation method of the antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP comprises the following steps: (1) Preparation of hydroxyapatite: Ca(NO3)2·4H2O is added to anhydrous ethanol, and magnetic stirring is performed at 60°C until uniform, then phosphorus pentoxide is slowly added and stirring is continued until a sol is formed, and the sol is gelled at room temperature, the formed gel is dried at 80°C for 24 hours, and then calcined at 700°C for 3 hours to obtain HAP; (2) Preparation of HAP@PDA-HDTBP: 1g of HAP and 2g of dopamine hydrochloride are added to 400 mL of Tris buffer, then 100 mL of anhydrous ethanol is added, ultrasonic treatment is performed for 1 hour, then HAP@PDA is obtained by filtration and drying, then 2g of HAP@PDA and 1g of hexadecyl tributyl phosphonium bromide are added to 200 mL of 95% ethanol aqueous solution, ultrasonic treatment is performed for 1 hour, then stirring is performed at 80°C for 6 hours; after the reaction is completed, the product is filtered and washed with ethanol and deionized water, and then vacuum dried at 60°C for 24 hours to obtain HAP@PDA-HDTBP; (3) Preparation of Mn-CeO2 / HAP@PDA-HDTBP: 125 mL of 1.33 mol / L NaOH aqueous solution is gradually added to 125 mL of 0.44 mol / L manganese acetate aqueous solution under continuous stirring, then 1.76g of Ce(NO3)3·6H2O and 8.9g of HAP@PDA-HDTBP are added, and finally the obtained suspension is transferred to a hydrothermal reactor for hydrothermal reaction; after the reaction is completed and the temperature is cooled to room temperature, the product is centrifuged and washed with deionized water and ethanol several times, and then vacuum dried at 60°C for 4 hours to obtain Mn-CeO2 / HAP@PDA-HDTBP.

2. The antibacterial PE composite material according to claim 1, characterized in that: In step (1), the mass ratio of phosphorus pentoxide to Ca(NO3)2·4H2O is 1:3.

3.

3. The antibacterial PE composite material according to claim 1, characterized in that: In step (3), the temperature of the hydrothermal reaction is 100°C, and the time is 10 hours.

4. A method of preparing an antibacterial PE composite material as claimed in any one of claims 1 to 3, characterized in that: The method comprises the following steps: (1) The antibacterial agent Mn-CeO2 / HAP@PDA-HDTBP is uniformly mixed with glycerol, antioxidant 1010, and polyethylene wax, then added to a high-speed stirrer, and then uniformly mixed with PE, and then dried at 60°C for 1 hour; (2) The dried material in step (1) is added to a twin-screw extruder, and then extruded and granulated to obtain a master batch; (3) The master batch obtained in step (2) is dried in a vacuum drying box, and then injection molded to obtain the antibacterial PE composite material.

5. The method of claim 4, wherein: In step (1), the rotation speed of the high-speed stirrer is 300r / min, and the temperature is 60°C.

6. The method of claim 4, wherein: The extrusion temperature of the double screw extruder in step (2) is: 220℃ for the first section, 215℃ for the second section, 210℃ for the third section, 205℃ for the fourth section, and 200℃ for the fifth section; the screw rotation speed is 10r / min.

7. The method of claim 4, wherein: The drying temperature in step (3) is 60℃, and the time is 1 hour; when injection molding, the injection molding temperature from the feeding port to the discharging port is: 250℃ for the first section, 240℃ for the second section, 230℃ for the third section, 220℃ for the fourth section, and 210℃ for the fifth section, the injection pressure is 135MPa, and the pressure maintaining pressure is 40MPa.

Images