A PEF / PBAT composite antibacterial material and its preparation method

Abstract

The present invention discloses a PEF / PBAT composite antibacterial material and a preparation method thereof, belonging to the technical field of preparation of functional polymer materials. The PEF / PBAT composite antibacterial material is prepared by melt blending polybutylene adipate terephthalate as a raw material, polyethylene 2,5-furandicarboxylate as a reinforcing agent, polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver complex as a compatibilizer and antibacterial agent. The PEF / PBAT composite antibacterial material prepared by the present invention has high tensile strength, large elongation at break, excellent antibacterial properties and complete biodegradability. It is mainly used in the fields of medical care, clothing, automobiles, food packaging, etc., and has significant economic value and social benefits.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of functional polymer materials, and specifically relates to a PEF / PBAT composite antibacterial material and a preparation method thereof. Background Art

[0002] Amidst the energy crisis of increasingly scarce petroleum resources and the severe ecological challenges posed by "white plastic pollution," replacing petroleum products with renewable, biodegradable polymers has become an urgent need and an inevitable trend in energy development. Polybutylene adipate terephthalate (PBAT) is a fully biodegradable aliphatic-aromatic copolyester. Due to its flexible, long-chain aliphatic hydrocarbon segments and rigid aromatic ring segments, PBAT exhibits excellent flexibility, making it a highly active biodegradable polymer in research and a promising market. However, PBAT's low mechanical strength, slow crystallization rate, and poor antimicrobial properties limit its application in medical, apparel, automotive, and food packaging applications. Poly(ethylene 2,5-furandicarboxylate) (PEF), composed of aliphatic hydrocarbons and cyclic conjugated dihydroxyaromatic compounds, is also a biodegradable polymer, offering advantages such as high rigidity and mechanical strength. Melt blending of PEF and PBAT is one of the effective ways to improve the mechanical strength of PBAT. However, PEF and PBAT have poor compatibility, so the effect of PEF on improving the mechanical strength of PBAT is limited. Summary of the Invention

[0003] This invention addresses the poor compatibility of PEF and PBAT, as well as the lack of antibacterial properties of PBAT, by providing a PEF / PBAT antibacterial composite material and its preparation method. The resulting PEF / PBAT antibacterial composite material exhibits high tensile strength, high elongation at break, excellent antibacterial properties, and complete biodegradability. It is primarily used in the medical, apparel, automotive, and food packaging industries, offering significant economic and social benefits.

[0004] To achieve the above object, the present invention adopts the following technical solutions:

[0005] A PEF / PBAT composite antibacterial material is prepared by melt blending polybutylene adipate terephthalate as raw material, polyethylene 2,5-furandicarboxylate as reinforcing agent, and polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite as compatibilizer and antibacterial agent.

[0006] The preparation method of the PEF / PBAT composite antibacterial material comprises the following steps:

[0007] (1) 50-150 g of 2,5-furandicarboxylic acid, 0.1-0.2 g of stannous oxalate, and 0.05-0.25 g of trimethyl phosphate were added to 50-120 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 200-240 °C for 2-6 h under nitrogen protection, and then evacuated to a vacuum degree of 10-200 Pa. The mixture was mechanically stirred at 220-260 °C for 3-7 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0008] (2) First, add 30-70 g of zinc oxide to 300-500 mL of ethanol and ultrasonically disperse it at room temperature for 30-60 min. Then, add 100-150 mL of 0.1 mol / L silver nitrate solution and 100-150 mL of 0.1 mol / L sodium bicarbonate solution in sequence. Stir magnetically at 70-100 °C for 4-8 h. After cooling, washing, drying, and heat treatment at 500-700 °C for 2-4 h, a zinc oxide / nanosilver composite is obtained.

[0009] (3) First, 30-70 g of zinc oxide / nanosilver composite was added to 400-600 mL of ethanol, and ultrasonically dispersed at room temperature for 30-60 min. Then, 2-5 g of bis(dioctylpyrophosphate)ethylene titanate was added and magnetically stirred at 70-100 °C for 2-4 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained.

[0010] (4) 20-100 g of 2,5-furandicarboxylic acid, 0.05-0.15 g of stannous oxalate, and 0.02-0.1 g of trimethyl phosphate were added to 20-80 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 200-240 °C for 30-90 min under nitrogen protection. Then, 40-100 g of polybutylene adipate terephthalate was added. The mixture was mechanically stirred at 200-240 °C for 30-90 min, and then vacuumed to a vacuum degree of 10-200 Pa. The mixture was mechanically stirred at 220-260 °C for 1-5 h. Finally, 10-50 g of surface-modified zinc oxide / nanosilver composite was added. The mixture was vacuumed to a vacuum degree of 10-200 Pa. The mixture was mechanically stirred at 220-260 °C for 10-30 min. min, cooling, washing and drying to obtain polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite;

[0011] (5) 20-40 g of polybutylene adipate terephthalate, 5-20 g of polyethylene 2,5-furandicarboxylate and 1-10 g of polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite were sequentially added into an internal mixer at a mixing temperature of 200-240 °C, a mixing pressure of 0.1-0.4 MPa, a rotor speed of 40-60 r / min and a mixing time of 6-12 min. The mixed material was cooled and crushed to obtain the PEF / PBAT composite antibacterial material.

[0012] The beneficial effects of the present invention are:

[0013] (1) The present invention adopts a direct esterification method to prepare a polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite having both a volume-increasing and antibacterial effect. The composite is added to a melt blend of polyethylene 2,5-furandicarboxylate and polybutylene adipate terephthalate. This can solve the problem of poor compatibility between the two, and can also solve the problem of easy agglomeration of zinc oxide / nanosilver antibacterial agents when added alone to the blend. At the same time, the direct esterification method has the advantages of high quality of the synthesized product, short production cycle, and low raw material usage.

[0014] (2) In the process of preparing the polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite, the present invention adds polyethylene terephthalate to the reaction system, first mechanically stirs the system at high temperature for a period of time, and then evacuates the system. This is conducive to the high-temperature hydrolysis of polyethylene terephthalate, reducing the molecular chain length, making the molecular chain segment lengths of polyethylene 2,5-furandicarboxylate and polybutylene adipate terephthalate in the composite more uniform, and better playing the role of the composite compatibilizer.

[0015] (3) The polybutylene adipate terephthalate, polyethylene 2,5-furandicarboxylate and polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite used in the present invention are all biodegradable polymer materials. Therefore, the PEF / PBAT composite antibacterial material prepared in the present invention is an environmentally friendly and completely biodegradable polymer material, which conforms to the national environmental protection concept and meets the requirements of sustainable development.

[0016] (4) The PEF / PBAT composite antibacterial material prepared by the present invention has high tensile strength, large elongation at break, excellent antibacterial property and complete biodegradability. The tensile strength is 25.8~28.5 MPa, the elongation at break is 209~260%, and the antibacterial rate is 94.7~96.8%. It can be used in the fields of medical treatment, clothing, automobile, and food packaging, and has significant economic value and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the infrared absorption spectrum of polyethylene 2,5-furandicarboxylate prepared in Example 1;

[0018] Figure 2 This is a hydrogen nuclear magnetic resonance spectrum of the polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite prepared in Example 1;

[0019] Figure 3 This is the infrared absorption spectrum of the polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite prepared in Example 1. DETAILED DESCRIPTION

[0020] The advantages and effects of the preparation method of the PEF / PBAT composite antibacterial material in this embodiment are further described below through several sets of examples and comparative examples. It should be understood that the specific embodiments described herein are only used to illustrate the present invention and are not intended to limit the present invention.

[0021] Example 1

[0022] (1) 100 g of 2,5-furandicarboxylic acid, 0.15 g of stannous oxalate, and 0.15 g of trimethyl phosphate were added to 85 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 4 h under nitrogen protection, then evacuated to a vacuum degree of 100 Pa, and mechanically stirred at 240 °C for 5 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0023] (2) First, 50 g of zinc oxide was added to 400 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 125 mL of 0.1 mol / L silver nitrate solution and 125 mL of 0.1 mol / L sodium bicarbonate solution were added in sequence. The mixture was magnetically stirred at 85 °C for 6 h. After cooling, washing, drying, and heat treatment at 600 °C for 3 h, a zinc oxide / nanosilver composite was obtained.

[0024] (3) First, 50 g of zinc oxide / nanosilver composite was added to 500 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 3.5 g of bis(dioctylpyrophosphate)ethylene titanate was added and magnetically stirred at 85 °C for 3 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained.

[0025] (4) 60 g of 2,5-furandicarboxylic acid, 0.1 g of stannous oxalate, and 0.06 g of trimethyl phosphate were added to 50 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 60 min under nitrogen protection. Then, 70 g of polybutylene adipate terephthalate was added. The mixture was mechanically stirred at 220 °C for 60 min, evacuated to a vacuum degree of 100 Pa, and mechanically stirred at 240 °C for 3 h. Finally, 30 g of surface-modified zinc oxide / nanosilver composite was added. The mixture was vacuumed to a vacuum degree of 100 Pa, and mechanically stirred at 240 °C for 20 min. After cooling, washing, and drying, a poly(ethylene 2,5-furandicarboxylate)-polybutylene adipate terephthalate)-zinc oxide / nanosilver composite was obtained.

[0026] (5) 30 g of polybutylene adipate terephthalate, 12 g of polyethylene 2,5-furandicarboxylate and 5 g of polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite were added into an internal mixer in sequence. The internal mixing temperature was 220 °C, the internal mixing pressure was 0.25 MPa, the rotor speed was 50 r / min, and the internal mixing time was 9 min. The internal mixing material was cooled and crushed to obtain the PEF / PBAT composite antibacterial material.

[0027] Figure 1 This is the infrared absorption spectrum of polyethylene 2,5-furandicarboxylate prepared in this example. As shown in the figure, 3440 cm -1 The stretching vibration peak of the polymer terminal hydroxyl group is 2970 cm -1 and 2780 cm -1 The stretching vibration peak of methylene CH is at 1720 cm -1 and 1150 cm -1 The stretching vibration peak of ester bond CO is 1580 cm -1 、1530 cm -1 and 1460 cm -1 The characteristic absorption peak of furan ring is at 1220 cm -1 The peaks at the bottom are the stretching vibration peaks of the furan ring -COC-, which indicate that polyethylene 2,5-furandicarboxylate was successfully prepared.

[0028] Figure 2This is the H NMR spectrum of the polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite prepared in this example. As can be seen from the figure, the chemical shift at 7.22 ppm belongs to the proton hydrogen on the furan ring, the chemical shift at 4.64 ppm belongs to the proton hydrogen of the methylene group in ethylene 2,5-furandicarboxylate, the chemical shifts at 4.52 ppm and 4.15 ppm belong to the protons of the methylene groups in the D, E, G, and F units, and the chemical shifts at 1.26 ppm and 0.88 ppm belong to the protons at the end of the long-chain alkane in the modified zinc oxide / nanosilver composite. These results indicate that the polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite was successfully prepared.

[0029] Figure 3 This is the infrared absorption spectrum of the polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite prepared in this example. As can be seen from the figure, 1580 cm -1 The characteristic peak of furan ring is at 1220 cm -1 The stretching vibration peak of -COC- on the furan ring is at 486 cm -1 The peaks at the bottom are the Zn-O bending vibration peaks on zinc oxide, which indicate that the polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite was successfully prepared.

[0030] Example 2

[0031] (1) 50 g of 2,5-furandicarboxylic acid, 0.1 g of stannous oxalate, and 0.05 g of trimethyl phosphate were added to 50 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 200 °C for 6 h under nitrogen protection, then evacuated to a vacuum degree of 10 Pa, and mechanically stirred at 260 °C for 3 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0032] (2) First, 30 g of zinc oxide was added to 300 mL of ethanol and ultrasonically dispersed at room temperature for 30 min. Then, 100 mL of 0.1 mol / L silver nitrate solution and 100 mL of 0.1 mol / L sodium bicarbonate solution were added in sequence. The mixture was magnetically stirred at 70 °C for 8 h. After cooling, washing, drying, and heat treatment at 500 °C for 4 h, a zinc oxide / nanosilver composite was obtained.

[0033] (3) First, 30 g of zinc oxide / nanosilver composite was added to 400 mL of ethanol and ultrasonically dispersed at room temperature for 30 min. Then, 2 g of bis(dioctylpyrophosphate)ethylene titanate was added and magnetically stirred at 70 °C for 4 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained.

[0034] (4) 20 g of 2,5-furandicarboxylic acid, 0.05 g of stannous oxalate, and 0.02 g of trimethyl phosphate were added to 20 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 200 °C for 90 min under nitrogen protection. Then, 40 g of polybutylene adipate terephthalate was added. The mixture was mechanically stirred at 200 °C for 90 min, evacuated to a vacuum degree of 10 Pa, and mechanically stirred at 260 °C for 1 h. Finally, 10 g of surface-modified zinc oxide / nanosilver composite was added. The mixture was vacuumed to a vacuum degree of 10 Pa, and mechanically stirred at 260 °C for 10 min. After cooling, washing, and drying, a poly(ethylene 2,5-furandicarboxylate)-polybutylene adipate terephthalate)-zinc oxide / nanosilver composite was obtained.

[0035] (5) 20 g of polybutylene adipate terephthalate, 5 g of polyethylene 2,5-furandicarboxylate and 1 g of polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite were added into an internal mixer in sequence. The internal mixing temperature was 200 °C, the internal mixing pressure was 0.1 MPa, the rotor speed was 40 r / min, and the internal mixing time was 12 min. The internal mixing material was cooled and crushed to obtain the PEF / PBAT composite antibacterial material.

[0036] Example 3

[0037] (1) 150 g of 2,5-furandicarboxylic acid, 0.2 g of stannous oxalate, and 0.25 g of trimethyl phosphate were added to 120 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 240 °C for 2 h under nitrogen protection, then evacuated to a vacuum degree of 200 Pa, and mechanically stirred at 220 °C for 7 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0038] (2) First, 70 g of zinc oxide was added to 500 mL of ethanol and ultrasonically dispersed at room temperature for 60 min. Then, 150 mL of 0.1 mol / L silver nitrate solution and 150 mL of 0.1 mol / L sodium bicarbonate solution were added in sequence. The mixture was magnetically stirred at 100 °C for 4 h. After cooling, washing, drying, and heat treatment at 700 °C for 2 h, a zinc oxide / nanosilver composite was obtained.

[0039] (3) First, 70 g of zinc oxide / nanosilver composite was added to 600 mL of ethanol and ultrasonically dispersed at room temperature for 60 min. Then, 5 g of bis(dioctylpyrophosphate)ethylene titanate was added and magnetically stirred at 100 °C for 2 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained.

[0040] (4) 100 g of 2,5-furandicarboxylic acid, 0.15 g of stannous oxalate, and 0.1 g of trimethyl phosphate were added to 80 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 240 °C for 30 min under nitrogen protection. Then 100 g of polybutylene adipate terephthalate was added. The mixture was mechanically stirred at 240 °C for 30 min, evacuated to a vacuum degree of 200 Pa, and mechanically stirred at 220 °C for 5 h. Finally, 50 g of surface-modified zinc oxide / nanosilver composite was added. The mixture was vacuumed to a vacuum degree of 200 Pa, and mechanically stirred at 220 °C for 30 min. After cooling, washing, and drying, a poly(ethylene 2,5-furandicarboxylate)-polybutylene adipate terephthalate)-zinc oxide / nanosilver composite was obtained.

[0041] (5) 40 g of polybutylene adipate terephthalate, 20 g of polyethylene 2,5-furandicarboxylate and 10 g of polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite were added into an internal mixer in sequence. The internal mixing temperature was 240 °C, the internal mixing pressure was 0.4 MPa, the rotor speed was 60 r / min, and the internal mixing time was 6 min. The internal mixing material was cooled and crushed to obtain the PEF / PBAT composite antibacterial material.

[0042] Comparative Example 1

[0043] (1) 100 g of 2,5-furandicarboxylic acid, 0.15 g of stannous oxalate, and 0.15 g of trimethyl phosphate were added to 85 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 4 h under nitrogen protection, then evacuated to a vacuum degree of 100 Pa, and mechanically stirred at 240 °C for 5 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0044] (2) First, 50 g of zinc oxide was added to 400 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 125 mL of 0.1 mol / L silver nitrate solution and 125 mL of 0.1 mol / L sodium bicarbonate solution were added in sequence. The mixture was magnetically stirred at 85 °C for 6 h. After cooling, washing, drying, and heat treatment at 600 °C for 3 h, a zinc oxide / nanosilver composite was obtained.

[0045] (3) First, 50 g of zinc oxide / nanosilver composite was added to 500 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 3.5 g of bis(dioctylpyrophosphate)ethylene titanate was added and magnetically stirred at 85 °C for 3 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained.

[0046] (4) 60 g of 2,5-furandicarboxylic acid, 0.1 g of stannous oxalate, and 0.06 g of trimethyl phosphate were added to 50 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 60 min under nitrogen protection. Then 70 g of polybutylene adipate terephthalate was added, and the mixture was evacuated to a vacuum degree of 100 Pa. The mixture was mechanically stirred at 240 °C for 3 h. Finally, 30 g of surface-modified zinc oxide / nanosilver composite was added, the mixture was evacuated to a vacuum degree of 100 Pa, and the mixture was mechanically stirred at 240 °C for 20 min. After cooling, washing, and drying, a poly(ethylene 2,5-furandicarboxylate)-polybutylene adipate terephthalate)-zinc oxide / nanosilver composite was obtained.

[0047] (5) 30 g of polybutylene adipate terephthalate, 12 g of polyethylene 2,5-furandicarboxylate and 5 g of polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite were added into an internal mixer in sequence. The internal mixing temperature was 220 °C, the internal mixing pressure was 0.25 MPa, the rotor speed was 50 r / min, and the internal mixing time was 9 min. The internal mixing material was cooled and crushed to obtain the finished product.

[0048] Comparative Example 2

[0049] (1) 100 g of 2,5-furandicarboxylic acid, 0.15 g of stannous oxalate, and 0.15 g of trimethyl phosphate were added to 85 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 4 h under nitrogen protection, then evacuated to a vacuum degree of 100 Pa, and mechanically stirred at 240 °C for 5 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0050] (2) First, 50 g of zinc oxide was added to 400 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 125 mL of 0.1 mol / L silver nitrate solution and 125 mL of 0.1 mol / L sodium bicarbonate solution were added in sequence. The mixture was magnetically stirred at 85 °C for 6 h. After cooling, washing, drying, and heat treatment at 600 °C for 3 h, a zinc oxide / nanosilver composite was obtained.

[0051] (3) First, 50 g of zinc oxide / nanosilver composite was added to 500 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 3.5 g of bis(dioctylpyrophosphate)ethylene titanate was added and magnetically stirred at 85 °C for 3 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained.

[0052] (4) 60 g of 2,5-furandicarboxylic acid, 0.1 g of stannous oxalate, and 0.06 g of trimethyl phosphate were added to 50 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 60 min under nitrogen protection. Then 70 g of polybutylene adipate terephthalate was added. The mixture was mechanically stirred at 220 °C for 60 min, and then evacuated to a vacuum degree of 100 Pa. The mixture was mechanically stirred at 240 °C for 3 h. After cooling, washing, and drying, a poly(ethylene 2,5-furandicarboxylate)-poly(butylene adipate terephthalate) composite was obtained.

[0053] (5) 30 g of polybutylene adipate terephthalate, 12 g of polyethylene 2,5-furandicarboxylate, 4.3 g of polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate composite and 0.7 g of surface-modified zinc oxide / nanosilver composite were added into an internal mixer in sequence. The internal mixing temperature was 220 °C, the internal mixing pressure was 0.25 MPa, the rotor speed was 50 r / min, and the internal mixing time was 9 min. The internal mixing material was cooled and crushed to obtain the finished product.

[0054] Comparative Example 3

[0055] (1) 100 g of 2,5-furandicarboxylic acid, 0.15 g of stannous oxalate, and 0.15 g of trimethyl phosphate were added to 85 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 4 h under nitrogen protection, then evacuated to a vacuum degree of 100 Pa, and mechanically stirred at 240 °C for 5 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0056] (2) First, 50 g of zinc oxide was added to 400 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 125 mL of 0.1 mol / L silver nitrate solution and 125 mL of 0.1 mol / L sodium bicarbonate solution were added in sequence. The mixture was magnetically stirred at 85 °C for 6 h. After cooling, washing, drying, and heat treatment at 600 °C for 3 h, a zinc oxide / nanosilver composite was obtained.

[0057] (3) First, 50 g of zinc oxide / nanosilver composite was added to 500 mL of ethanol and ultrasonically dispersed at room temperature for 45 min. Then, 3.5 g of bis(dioctylpyrophosphate)ethylene titanate was added and magnetically stirred at 85 °C for 3 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained.

[0058] (4) 30 g of polybutylene adipate terephthalate, 12 g of polyethylene 2,5-furandicarboxylate and 0.7 g of surface-modified zinc oxide / nanosilver composite were added into an internal mixer in sequence. The internal mixing temperature was 220 °C, the internal mixing pressure was 0.25 MPa, the rotor speed was 50 r / min, and the internal mixing time was 9 min. The internal mixing material was cooled and crushed to obtain the finished product.

[0059] Comparative Example 4

[0060] (1) 100 g of 2,5-furandicarboxylic acid, 0.15 g of stannous oxalate, and 0.15 g of trimethyl phosphate were added to 85 g of ethylene glycol in sequence. The mixture was first mechanically stirred at 220 °C for 4 h under nitrogen protection, then evacuated to a vacuum degree of 100 Pa, and mechanically stirred at 240 °C for 5 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained.

[0061] (2) 30 g of polybutylene adipate terephthalate and 12 g of polyethylene 2,5-furandicarboxylate were added into an internal mixer in sequence. The internal mixing temperature was 220 °C, the internal mixing pressure was 0.25 MPa, the rotor speed was 50 r / min, and the internal mixing time was 9 min. The internal mixing material was cooled and crushed to obtain the finished product.

[0062] The products obtained from the three groups of examples and four groups of comparative examples were tested for tensile strength and elongation at break according to GB / T1040.2-2022, and for antibacterial performance according to the oscillation method in GB / T 20944.3-2008. The test results are shown in the following table.

[0063]

[0064] From the test results of the embodiments and comparative examples, it can be seen that a PEF / PBAT composite antibacterial material with high tensile strength, large elongation at break, excellent antibacterial property and complete biodegradability can be prepared by melt blending poly(butylene adipate terephthalate) as a raw material, poly(ethylene 2,5-furandicarboxylate) as a reinforcing agent, and poly(ethylene 2,5-furandicarboxylate)-poly(butylene adipate terephthalate)-zinc oxide / nanosilver composite as a compatibilizer and antibacterial agent.

[0065] The foregoing description shows and describes preferred embodiments of the present invention. As previously mentioned, it should be understood that the present invention is not limited to the form disclosed herein and should not be construed as excluding other embodiments. Instead, the present invention can be used in various other combinations, modifications, and environments and can be modified within the scope of the inventive concept described herein by the teachings above or by techniques or knowledge in the relevant art. Modifications and variations made by those skilled in the art without departing from the spirit and scope of the present invention are intended to be within the scope of the appended claims.

Claims

1. A method for preparing a PEF / PBAT composite antibacterial material, characterized by: The PEF / PBAT composite antibacterial material is prepared by melt blending polybutylene adipate terephthalate as a raw material, polyethylene 2,5-furandicarboxylate as a reinforcing agent, and polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite as a compatibilizer and antibacterial agent; The following steps are involved: (1) 50-150 g of 2,5-furandicarboxylic acid, 0.1-0.2 g of stannous oxalate, and 0.05-0.25 g of trimethyl phosphate were added to 50-120 g of ethylene glycol in sequence. Under nitrogen protection, the mixture was stirred at 200-240 °C for 2-6 h, vacuumed, and stirred at 220-260 °C for 3-7 h. After cooling, washing, and drying, polyethylene 2,5-furandicarboxylate was obtained. (2) Add 30-70 g of zinc oxide to 300-500 mL of ethanol and disperse under ultrasonication for 30-60 min. Then, add 100-150 mL of 0.1 mol / L silver nitrate solution and 100-150 mL of 0.1 mol / L sodium bicarbonate solution in sequence. Stir magnetically at 70-100 °C for 4-8 h. Cool, wash, dry, and heat-treat at 500-700 °C for 2-4 h to obtain a zinc oxide / nanosilver composite. (3) Add 30-70 g of zinc oxide / nanosilver composite to 400-600 mL of ethanol, ultrasonically disperse for 30-60 min, then add 2-5 g of bis(dioctyl pyrophosphate)ethylene titanate, and stir magnetically at 70-100 °C for 2-4 h. After cooling, washing, drying, grinding, and sieving, a surface-modified zinc oxide / nanosilver composite was obtained. (4) 20-100 g of 2,5-furandicarboxylic acid, 0.05-0.15 g of stannous oxalate, and 0.02-0.1 g of trimethyl phosphate were added to 20-80 g of ethylene glycol in sequence, and stirred at 200-240 °C for 30-90 min under nitrogen protection. Then, 40-100 g of polybutylene adipate terephthalate was added, and the mixture was stirred at 200-240 °C for 30-90 min. The mixture was vacuumed and stirred at 220-260 °C for 1-5 h. Then, 10-50 g of surface-modified zinc oxide / nanosilver composite was added, and the mixture was vacuumed and stirred at 220-260 °C for 10-30 min. After cooling, washing, and drying, a poly(ethylene 2,5-furandicarboxylate)-polybutylene adipate terephthalate)-zinc oxide / nanosilver composite was obtained. (5) 20-40 g of polybutylene adipate terephthalate, 5-20 g of polyethylene 2,5-furandicarboxylate and 1-10 g of polyethylene 2,5-furandicarboxylate-polybutylene adipate terephthalate-zinc oxide / nanosilver composite were sequentially added into an internal mixer at a mixing temperature of 200-240 °C, a mixing pressure of 0.1-0.4 MPa, a rotor speed of 40-60 r / min and a mixing time of 6-12 min. The mixed material was cooled and crushed to obtain the PEF / PBAT composite antibacterial material.

2. A PEF / PBAT composite antibacterial material prepared by the method according to claim 1.

Images