Antibacterial polyethylene metal polymeric material as well as preparation method and application thereof

Abstract

The invention relates to an antibacterial polyethylene metal polymeric material as well as a preparation method and application thereof. The antibacterial polyethylene metal polymeric material is a polyethylene copper ion polymer which is formed by CuCl2 and a polyethylene copolymer represented by a formula # imgabs 0 # and is represented by a formula # imgabs 1 #; or a polyethylene zinc ion polymer represented by the formula # imgabs3 # formed by ZnCl2 and a polyethylene copolymer represented by the formula # imgabs2 #; or a polyethylene silver ion polymer represented by a formula # imgabs5 # formed by AgNO3 and a polyethylene copolymer represented by a formula # imgabs4 #; or a polyethylene iron ion polymer represented by the formula # imgabs7 # formed from FeCl3 and a polyethylene copolymer represented by the formula # imgabs6 #, wherein x, y, n are as defined herein. The antibacterial polyethylene metal material can be simply and rapidly prepared under mild conditions, has excellent antibacterial performance and mechanical performance, can be widely applied to the fields of medical instruments, food packaging, daily necessities and the like, effectively reduces propagation of microorganisms such as bacteria and the like, and guarantees public health safety.

Description

Technical Field

[0001] The invention belongs to the field of high molecular polyolefin metal polymer materials, and in particular relates to polyolefin metal materials and a preparation method and application thereof. Background Art

[0002] With the improvement of the quality of life in modern society, people's awareness of health and hygiene has gradually strengthened, and the demand for daily necessities materials that can reduce and isolate the spread of viruses is increasing. Especially in the fields of biomedicine, food packaging, textile daily necessities, etc., the use of antibacterial materials can effectively block the spread of bacteria and viruses, and reduce the risk of public health disease transmission and cross infection. The harm of traditional chemical disinfectants to the environment and potential health threats have prompted people to look for safe, non-toxic and sustainable alternative products. Consumers' demand for higher quality and safer products has promoted the research and development of antibacterial materials.

[0003] The production of polyethylene usually relies on fossil fuels, and its products are widely used in all aspects of society. However, polyethylene products are difficult to degrade, and the resulting plastic waste and microplastics will cause certain pollution and harm to the natural environment. Therefore, the recycling and sustainable use of polyethylene materials is also an environmental issue that needs to be solved urgently.

[0004] The development of materials science and synthetic chemistry technology has made it possible to effectively load antimicrobial agents in polyethylene. By introducing antibacterial groups on the polyethylene surface through blending and plasma treatment technology, the growth of bacteria on the polyethylene surface can be effectively inhibited, and the antibacterial properties and durability of the material can be enhanced. By adding metal compounds or metal ions with antibacterial properties such as silver ions and zinc ions to polyethylene to synthesize antibacterial metal polyethylene polymer materials, the polyethylene material is given a new antibacterial function, the use of additional antibacterial layers or packaging materials is reduced, and the full utilization of polyethylene products is achieved.

[0005] In particular, antibacterial materials prepared by nanotechnology, such as metal oxide nanoparticles such as nanosilver and nanozinc oxide, which have been widely studied in recent years, have higher surface area and activity, which improves the antibacterial effect and stability of polyethylene antibacterial materials. However, the antibacterial effect of nanometal materials usually depends on the metal ions released or the oxides produced, and their release efficiency changes with temperature, pH and time. In addition, the construction process of nanocarriers is complicated. Their high surface energy and activity may have toxic side effects on human cells. When used in food and medical fields, biosafety and environmental risk assessments are required. Although nanometal materials show potential in the antibacterial field, there are still challenges in the research and regulatory needs of their safety and environmental impact. On the other hand, the antibacterial materials prepared by blending antibacterial agents into the materials still have the problem of incompatibility between antibacterial agents and polyethylene materials, which leads to the deterioration of the performance of polyethylene materials. Therefore, in order to overcome the above problems, it is of great significance to prepare a new polyethylene metal antibacterial material with simple production process, good stability, long-lasting antibacterial effect, low cost and strong universality. Summary of the invention

[0006] Based on the above discussion, one purpose of the present invention is to design and synthesize a series of polyethylene metal polymer materials with strong antibacterial properties. The synthesis method of the material is simple and has significant antibacterial properties.

[0007] Another object of the present invention is to provide four polyethylene metal polymer materials and preparation methods thereof, and the polyethylene metal polymer materials can be used as biomedical devices, food packaging, and personal care products.

[0008] The technical solution adopted by the present invention is summarized as follows:

[0009] Four methods for synthesizing polyethylene metal polymer materials are firstly synthesized by polymerization reaction with the formula The polyethylene material PE-UA containing carboxylic acid groups is represented. PE-UA is a copolymer of ethylene and 10-undecenoic acid (UA), which can be simply and effectively synthesized under mild conditions. The -COOH in the obtained ethylene-10-undecenoic acid polymer PE-UA reacts with different metal salts to anchor metal ions on the polyethylene functional group -COOH. Specifically, four polyethylene metal polymers are involved, and their structural formulas are as follows:

[0010] 1. By The polyethylene copper ion polymer P-COOH-Cu is represented; 2. By formula The polyethylene zinc ion polymer P-COOH-Zn is represented; 3. By formula The polyethylene silver ion polymer P-COOH-Ag is represented; 4. By The polyethylene iron ion polymer P-COOH-Fe is represented;

[0011] Wherein, x is an integer from 20 to 2000; y is an integer from 1 to 20; and n is an integer from 20 to 2000.

[0012] —: refers to covalent bond or coordination bond.

[0013] The four metal compounds used in the present invention are: CuCl2, ZnCl2, AgNO3, and FeCl3.

[0014] Among them, in the reaction of synthesizing four polyethylene metal polymers, P-COOH-Cu: every two -COOH and one Cu 2+ Coordination, the amount of CuCl2 is 1 / 2 of the UA content. P-COOH-Zn: Every two -COOH and one Zn 2+ For coordination, the amount of ZnCl2 used is 1 / 2 of the UA content. P-COOH-Ag: Each -COOH with one Ag + For coordination, the amount of AgNO3 used is the same as the UA content. P-COOH-Fe: Every three -COOH and one Fe 3+ To prevent Fe 3+ Too much will lead to polymer crosslinking. Preferably, the amount of FeCl3 used is 1 / 18 of the UA content.

[0015] In summary, in the present invention, The carboxylic acid polyethylene polymer PE-UA can introduce a variety of antibacterial groups with antibacterial effects such as metal ions or metal compounds to synthesize corresponding polyethylene metal polymers, and has good antibacterial properties.

[0016] In another aspect, the present invention provides a method for preparing the above-mentioned polyethylene metal polymer material, the method comprising: in a chlorobenzene (or toluene, 1,2-dichlorobenzene, tetrahydrofuran) solvent at a temperature of 50-150°C, The polyethylene copolymer represented by is reacted with CuCl2, ZnCl2, AgNO3, and FeCl3 for 1-24 hours to obtain A polyethylene metal ion polymer represented by, wherein x is an integer of 20 to 2000; y is an integer of 1 to 20; and n is an integer of 20 to 2000.

[0017] A series of novel polyethylene metal polymer materials with antibacterial function can be obtained by the above-mentioned preparation method.

[0018] In addition, the present invention uses the formula The ethylene-10-undecenoic acid random copolymer can be simply and effectively prepared under mild conditions in the presence of a specific imine-amine nickel catalyst. The polar polyethylene material has a high polymer molecular weight, and its number average molecular weight is above 60,000. At the same time, the polydispersity index of the polar polyethylene material of the present invention is relatively narrow (roughly in the range of 1.4 to 1.6), and the insertion rate of the polar monomer 10-undecenoic acid is between 1.1 and 1.3%. Therefore, the material has certain mechanical properties.

[0019] In addition, the four polyethylene metal polymer materials synthesized by the present invention were respectively used for antibacterial experiments on Escherichia coli and Staphylococcus aureus. The antibacterial verification results showed that the antibacterial effects on Escherichia coli and Staphylococcus aureus were significant.

[0020] The present invention synthesizes four polyethylene metal polymer materials by reacting a simple structure of polyethylene acetate polymer with common inorganic compounds CuCl2, ZnCl2, AgNO3, and FeCl3 respectively. The antibacterial polyethylene material has chemical stability, low temperature resistance and processing performance, which can extend the service life of the product. The combination of these technologies not only gives polyethylene the characteristics of antibacterial function and improves the performance of the antibacterial material, but also reduces production costs, reduces the waste of polyethylene product resources, and avoids the disadvantages of directly adding antibacterial agents to polyethylene materials, making the antibacterial material more practical and economical. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The structural diagrams of four antibacterial polyolefin metal ion materials (structural diagrams of four polyethylene metal ion polymers) obtained according to the implementation examples of the present invention are shown.

[0022] Figure 2 A comparison chart of the tensile strength and elongation at break of the polar polyethylene material obtained according to the implementation case of the present invention and the prepared antibacterial polyolefin metal ion material is shown (a comparison chart of the stress-strain curves of the polar polyethylene material and the polyethylene metal ion material).

[0023] Figure 3 A comparison chart of the antibacterial effects of the polar polyethylene material obtained according to the implementation case of the present invention and the prepared antibacterial polyolefin metal ion material on Escherichia coli is shown (a chart showing the antibacterial effects of polyethylene metal polymers on Escherichia coli).

[0024] Figure 4A comparison chart of the antibacterial effects of the polar polyethylene material obtained according to the implementation case of the present invention and the prepared antibacterial polyolefin metal ion material on Staphylococcus aureus is shown (a chart showing the antibacterial effects of polyethylene metal polymers on Staphylococcus aureus). DETAILED DESCRIPTION

[0025] The present invention provides a method for synthesizing four polyethylene metal polymer materials, and after experimental verification, the four materials have good antibacterial properties. The present invention will be further described in conjunction with specific examples. It should be emphasized that the following examples are helpful for understanding the performance test of the present invention and polymer materials, but are not limited to the scope of the present invention. Those skilled in the art may make some non-essential modifications and adjustments based on the content of the invention, and improvements in equivalent forms also fall within the scope of protection of the claims attached to this application.

[0026] The present invention has no special requirements for the raw materials in the following embodiments, and professionals can purchase them from the market or prepare them according to the law.

[0027] After in-depth research, the inventors of the present invention unexpectedly found that, on the one hand, in the presence of an imine-amine nickel catalyst, catalytic direct copolymerization of ethylene and a polar monomer such as 10-undecenoic acid can obtain a polar polyolefin containing polar functional groups such as carboxyl groups with high molecular weight, equal insertion ratio and excellent mechanical properties; on the other hand, such a polar polyolefin and different metal ions can be used to efficiently prepare antibacterial polyolefin materials with antibacterial properties as well as high molecular weight and excellent mechanical properties under mild conditions.

[0028] In the present invention, the formula used is The polar polyethylene random copolymer represented by A random copolymer is obtained by copolymerizing an ethylene monomer represented by the formula CH2=CH2 and a polar olefin comonomer 10-undecenoic acid represented by the formula CH2=CH-(CH2)8-COOH in the presence of an imine-amine nickel catalyst and under the activation of a co-catalyst at a temperature of 25 to 120°C, wherein Ph represents a phenyl group.

[0029] More specifically, a polar olefin comonomer represented by the formula CH2=CH-(CH2)8-COOH, a solvent such as toluene, a cocatalyst such as diethylaluminum chloride (or ethylaluminum dichloride, triisobutylaluminum, etc.) and a desired imine-amine nickel catalyst are added to a polymerization reactor, a small amount of ethylene is introduced, the temperature is rapidly raised to a specified temperature, and the ethylene pressure is adjusted to a specified pressure. After a certain period of polymerization, a large amount of methanol is added to quench, and a white polymer is obtained by filtration. The residual monomer can be further removed by a Soxhlet extractor, thereby obtaining a polymer represented by the formula Represents a polar polyethylene random copolymer.

[0030] The imine-amine nickel catalyst used in the above preparation was independently designed and synthesized by the inventors according to the reported literature method (for example, see Inorg. Chem. 2023, 62, 5105-5113).

[0031] In the above preparation, the polymerization temperature is preferably 25-120°C, for example 25°C; the ethylene pressure is preferably 2-8 atmospheres (atm), more preferably 2-6atm; the concentration of the polar olefin comonomer represented by the formula CH2=CH-(CH2)8-COOH can be 0.01-10 mol / L, more preferably 0.1-2 mol / L; the polymerization time can be 0.1-12h, preferably 0.1-2h; the amount of imine-amine nickel catalyst can be 5-50μmol; the co-catalyst can be diethylaluminum chloride, ethylaluminum dichloride, triisobutylaluminum, etc., preferably, the co-catalyst is diethylaluminum chloride, and the amount of the co-catalyst is 1-1000 equivalents of the amount of the catalyst.

[0032] In the above preparation, the copolymerization reaction can be carried out in an additionally added organic solvent. Preferably, the organic solvent that can be used in the present invention is toluene, xylene, chlorobenzene, n-hexane, n-heptane or a mixture thereof. The present invention has no particular restrictions on the amount of solvent used, and can be appropriately adjusted as needed.

[0033] In the above preparation, there is no particular limitation on the reactor for achieving copolymerization, as long as the desired copolymerization reaction can be achieved. Preferably, the copolymerization reaction of the present invention can be carried out using an autoclave. More preferably, the reactor is in an inert gas environment such as argon.

[0034] Synthesis Example 1: Synthesis of antibacterial polyethylene metal ion materials

[0035] (1) Polar polyethylene random copolymer Preparation

[0036] In a glove box, under an argon atmosphere, 50 mL of toluene solvent was added to a 100 mL high-pressure reactor, followed by 6 mmol of diethylaluminum chloride, 12.5 mmol of polar monomer CH2=CH-(CH2)8-COOH, and 20 μmol of imine-amine nickel catalyst dissolved in 2 mL of dichloromethane was added to the reactor. Then, the ethylene gas source pipeline was connected to allow ethylene to pass into the reactor, and the ethylene pressure was adjusted to 2 atm. The reaction was carried out at 25°C for 30 min under magnetic stirring. After the reaction was completed, the reactor was opened, and 50 mL of ethanol acidified with hydrochloric acid was added to the obtained reaction solution for quenching. Finally, it was filtered under reduced pressure, and the obtained solid was dried in a vacuum drying oven at 50°C for 24 h to obtain 1.88 g of white polar polyethylene random copolymer.

[0037] through 1 The H NMR spectrum was measured in deuterated tetrachloroethane at 120°C, and the comonomer content of the obtained copolymer was 1.18%. The number average molecular weight (Mn) of the obtained copolymer was measured by high temperature gel permeation chromatography GPC (trichlorobenzene as solvent, measurement temperature of 150°C) and was 6.4×10 4 g·mol -1 , and the polydispersity index (PDI) is 1.55.

[0038] (2) Antibacterial polyethylene metal ion materials Preparation

[0039] 3.0 g of polar polyethylene copolymer Dissolve in 150 mL of chlorobenzene and stir for 3 hours at 110°C in an argon atmosphere. Then add 1 / 2 equivalent of CuCl2 in the copolymer carboxylic acid functional group in an argon atmosphere and react for another 3 hours. After the reaction is complete, drain the solvent and vacuum dry at 50°C to constant weight to obtain an antibacterial polyethylene metal ion material.

[0040] Synthesis Example 2: Synthesis of antibacterial polyethylene metal ion materials

[0041] 3.0 g of polar polyethylene copolymer Dissolve in 150 mL of chlorobenzene and stir for 3 hours at 110°C under argon atmosphere. Then add ZnCl2 with 1 / 2 equivalent of copolymer carboxylic acid functional group content under argon atmosphere and react for another 3 hours. After the reaction is completed, drain the solvent and vacuum dry at 50°C to constant weight to obtain antibacterial polyethylene metal ion material.

[0042] Synthesis Example 3: Synthesis of antibacterial polyethylene metal ion materials

[0043] 3.0 g of polar polyethylene copolymer Dissolve in 150 mL of chlorobenzene and stir for 3 hours at 110°C in an argon atmosphere. Then add an equal amount of AgNO3 with the same carboxylic acid functional group content in the copolymer in an argon atmosphere and react for another 3 hours. After the reaction is complete, drain the solvent and vacuum dry at 50°C to constant weight to obtain an antibacterial polyethylene metal ion material.

[0044] Synthesis Example 4: Synthesis of antibacterial polyethylene metal ion materials

[0045] 3.0 g of polar polyethylene copolymer Dissolve in 150 mL of chlorobenzene and stir for 3 hours at 110°C under argon atmosphere. Then add FeCl3 with 1 / 18 equivalent of copolymer carboxylic acid functional group content under argon atmosphere and react for another 3 hours. After the reaction is completed, drain the solvent and vacuum dry at 50°C to constant weight to obtain antibacterial polyethylene metal ion material.

[0046] Test synthesis example 1-4: Antibacterial performance test of Escherichia coli on control material and four antibacterial polyethylene metal materials

[0047] The antibacterial properties of the material were evaluated by the number of monoclonal colonies grown on the plate culture medium using the dilution coating method. First, the four samples of the present invention (antibacterial polyethylene metal materials prepared in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4) and the control material PE-UA were pressed to form a rectangular polyethylene film with a length of 4 mm, a width of 4 mm, and a thickness of 0.2 mm. The solid LB culture medium Escherichia coli strain was picked with an inoculation loop and inoculated into the liquid LB culture medium, and cultured overnight at 37°C constant temperature shaker and 200rpm for 10 hours. Then 40 μL of the overnight bacterial solution was taken in a 15mL centrifuge tube, diluted with 4mL LB culture medium, and cultured at 37oC shaker for 2 hours. Take the LB culture medium without bacterial solution as a blank, and detect the absorbance of the bacterial solution at a wavelength of 600nm in an ultraviolet spectrophotometer, so that the OD600 nm of the bacterial solution is measured to be 0.5-0.7, that is, the Escherichia coli reaches the logarithmic growth phase. The PE-UA control material, P-COOH-Cu, P-COOH-Zn, P-COOH-Ag, and P-COOH-Fe materials were sterilized by ultraviolet irradiation for 15 minutes. 10 μL of Escherichia coli in the logarithmic growth period was dropped on the material, covered with materials of the same size, and a 50g weight was pressed to make the material and the bacterial solution fully contact, and treated at room temperature for 30 minutes. After the treatment, all materials were transferred to a centrifuge tube with 10mL of sterile water and ultrasonicated for 20 minutes at 40KHz and 99% Power. Centrifuge at 4000rpm for 10min, discard the supernatant to 2mL, resuspend and blow evenly, take 100μL of bacterial suspension, add 900μL of sterile water, dilute 10×, 100× in sequence, inoculate PE-UA control material, P-COOH-Cu, P-COOH-Zn, P-COOH-Ag, P-COOH-Fe material with 100μL of diluted 100× concentration, spread on LB solid plate, place inverted in 37℃ incubator for 16 hours.

[0048] Figure 3 (a) shows the antibacterial effect of the control material PE-UA (obtained from the test results of Test Synthesis Examples 1-4, i.e., the control sample was used to treat Escherichia coli for 30 minutes, diluted 100× and then coated, and monoclonal colonies were visible on the solid plate culture medium after 16 hours of culture); Figure 3 (b), (c), (d), (e) are diagrams showing the antibacterial effects of the polyethylene metal polymers prepared according to Synthesis Examples 1, 2, 3, and 4, respectively, and (f) is a quantitative diagram of the antibacterial effect (obtained from the test results of Synthesis Examples 1-4 using the corresponding polyethylene metal polymers obtained by Synthesis Examples 1-4 of the present invention, i.e., using P-COOH-Cu, P-COOH-Zn, P-COOH-Ag, and P-COOH-Fe materials to treat Escherichia coli for 30 minutes, diluting 100× and then coating, and monoclonal colonies can be seen on the solid plate culture medium after culturing for 16 hours). Figure 3 The results show that compared with the PE-UA polyethylene material in the control group, the four polyethylene metal polymer materials of the present invention all exhibit significant antibacterial effects on Escherichia coli.

[0049] Test Synthesis Example 1-4: Antibacterial Performance Test of Control Material and Four Antibacterial Polyethylene Metal Materials against Staphylococcus aureus

[0050] The antibacterial properties of the material were evaluated by the number of monoclonal colonies grown on the plate culture medium using the dilution coating method. First, the four samples of the present invention (antibacterial polyethylene metal materials prepared in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4) and the control material PE-UA were pressed into films to make rectangular polyethylene films with a length of 4 mm, a width of 4 mm, and a thickness of 0.2 mm for standby use. The solid LB culture fund Staphylococcus aureus strain was picked up with an inoculation loop and inoculated into the liquid LB culture medium, and cultured overnight at 37°C constant temperature shaking table at 200rpm for 10 hours. Then 40 μL of the overnight bacterial solution was taken into a 15mL centrifuge tube, 4mL of LB culture medium was added for dilution, and cultured at 37°C shaking table for 2 hours. The LB culture medium without bacterial solution was taken as a blank, and the bacterial solution absorbance was detected at a wavelength of 600nm in an ultraviolet spectrophotometer, so that the OD600nm of the bacterial solution was measured to be 0.5-0.7, that is, Staphylococcus aureus reached the logarithmic growth phase. The PE-UA control material, P-COOH-Cu, P-COOH-Zn, P-COOH-Ag, and P-COOH-Fe materials were sterilized by ultraviolet irradiation for 15 minutes. 10 μL of Staphylococcus aureus in the logarithmic growth phase was dropped on the material, covered with a material of the same size, and a 50g weight was pressed to make the material and the bacterial solution fully contact, and treated at room temperature for 30 minutes. After the treatment, all materials were transferred to a centrifuge tube with 10mL of sterile water and ultrasonicated for 20 minutes at 40KHz and 99% Power. Centrifuge at 4000rpm for 10min, discard the supernatant to 2mL, resuspend and blow evenly, take 100μL of bacterial suspension, add 900μL of sterile water, dilute 10× and 100× in sequence, inoculate PE-UA control material, P-COOH-Cu, P-COOH-Zn, P-COOH-Ag, P-COOH-Fe with 100μL of diluted 100× concentration, spread on LB solid plate, and place it in a 37℃ incubator for inverted culture for 24 hours.

[0051] Figure 4 (a) shows the antibacterial effect of the control material PE-UA (obtained from the test results of Test Synthesis Examples 1-4, i.e., the control sample was used to treat Staphylococcus aureus for 30 minutes, diluted 100× and then coated, and monoclonal colonies were visible on the solid plate culture medium after 24 hours of culture); Figure 4 (b), (c), (d), (e) are diagrams showing the antibacterial effects of the polyethylene metal polymers prepared according to Synthesis Examples 1, 2, 3, and 4, respectively, and (f) is a quantitative diagram of the antibacterial effect (obtained from the test results of Synthesis Examples 1-4 using the corresponding polyethylene metal polymers obtained in Synthesis Examples 1-4 of the present invention, i.e., using P-COOH-Cu, P-COOH-Zn, P-COOH-Ag, and P-COOH-Fe materials to treat Staphylococcus aureus for 30 minutes, diluting 100× and then coating, and monoclonal colonies can be seen on the solid plate culture medium after culturing for 24 hours). Figure 4 The results show that compared with the PE-UA polyethylene material in the control group, the four polyethylene metal polymer materials of the present invention all exhibit significant antibacterial effects on Staphylococcus aureus.

[0052] It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. In addition, it should be understood that after reading the disclosure of the present invention, those skilled in the art can make various changes and modifications to the present invention, and these equivalent forms fall into the scope limited by the appended claims of the application equally.

Claims

1. An antibacterial polyethylene metal polymer material, the antibacterial polyethylene metal polymer material is composed of CuCl2 and The polyethylene copolymer represented by the formula A polyethylene copper ion polymer represented by: x is an integer from 20 to 2000; y is an integer from 1 to 20; n is an integer from 20 to 2000.

2. An antibacterial polyethylene metal polymer material, the antibacterial polyethylene metal polymer material is composed of ZnCl2 and The polyethylene copolymer represented by the formula A polyethylene zinc ionomer represented by x is an integer from 20 to 2000; y is an integer from 1 to 20; n is an integer from 20 to 2000.

3. An antibacterial polyethylene metal polymer material, the antibacterial polyethylene metal polymer material is composed of AgNO3 and a The polyethylene copolymer represented by the formula A polyethylene silver ion polymer, wherein: x is an integer from 20 to 2000; y is an integer from 1 to 20; n is an integer from 20 to 2000.

4. An antibacterial polyethylene metal polymer material, the antibacterial polyethylene metal polymer material is composed of FeCl3 and The polyethylene copolymer represented by the formula A polyethylene iron ion polymer, wherein: x is an integer from 20 to 2000; y is an integer from 1 to 20; n is an integer from 20 to 2000.

5. The antibacterial polyethylene metal polymer material according to claim 1, 2, 3, or 4, characterized in that: The metal ions are copper ions, zinc ions, silver ions and iron ions.

6. The antibacterial polyethylene metal polymer material according to claim 1, 2, 3, or 4, characterized in that: The formula The polyethylene copolymer represented by A random copolymer is obtained by copolymerizing an ethylene monomer represented by the formula CH2=CH2 and a polar olefin comonomer 10-undecenoic acid represented by the formula CH2=CH-(CH2)8-COOH in the presence of the shown imine-amine nickel catalyst at a temperature of 25 to 120°C, wherein Ph represents a phenyl group.

7. A method for preparing the antibacterial polyethylene metal polymer material according to claim 1, comprising: in a chlorobenzene (or toluene, 1,2-dichlorobenzene, tetrahydrofuran) solvent at a temperature of 50-150°C, The polyethylene copolymer represented by is reacted with CuCl2 for 1-24 hours to obtain a A polyethylene copper ion polymer represented by x, y, n are as defined in claim 1.

8. A method for preparing the antibacterial polyethylene metal polymer material according to claim 2, comprising: in a chlorobenzene (or toluene, 1,2-dichlorobenzene, tetrahydrofuran) solvent at a temperature of 50-150°C, The polyethylene copolymer represented by is reacted with ZnCl2 for 1-24 hours to obtain a A polyethylene zinc ion polymer represented by x, y, n are as defined in claim 2.

9. A method for preparing the antibacterial polyethylene metal polymer material according to claim 3, comprising: in a chlorobenzene (or toluene, 1,2-dichlorobenzene, tetrahydrofuran) solvent at a temperature of 50-150°C, The polyethylene copolymer represented by is reacted with AgNO3 for 1-24 hours to obtain A polyethylene silver ion polymer represented by x, y, n are as defined in claim 3.

10. A method for preparing the antibacterial polyethylene metal polymer material according to claim 4, comprising: in a chlorobenzene (or toluene, 1,2-dichlorobenzene, tetrahydrofuran) solvent at a temperature of 50-150°C, The polyethylene copolymer represented by is reacted with FeCl3 for 1-24 hours to obtain the A polyethylene iron ion polymer represented by x, y, n are as defined in claim 4.

11. Use of the antibacterial polyethylene metal polymer material according to any one of claims 1 to 4 as a biomedical device material, food packaging material or daily necessities material.

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