An environmentally friendly antibacterial PE material and its preparation method

Abstract

The present invention discloses an environmentally friendly antibacterial PE material and a preparation method thereof, relating to the technical field of polymer materials. When preparing the environmentally friendly antibacterial PE material of the present invention, sodium periodate is first used to oxidize cellulose to obtain oxidized cellulose, and the oxidized cellulose is reacted with 3-amino-1,2,4-triazole to obtain modified cellulose; acrylic acid is copolymerized during the ethylene polymerization process to obtain polyethylene containing carboxyl groups. After mixing, plasticizing and rolling the polyethylene containing carboxyl groups and the modified cellulose, chlorination treatment is carried out with sodium hypochlorite to obtain the environmentally friendly antibacterial PE material. The environmentally friendly antibacterial PE material prepared by the present invention has excellent antibacterial properties and tensile strength.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and specifically relates to an environmentally friendly antibacterial PE material and a preparation method thereof. Background Art

[0002] In recent years, with the acceleration of global food circulation, the spread range of foodborne pathogens has become wider and wider, and the incidence rate of foodborne diseases has gradually increased. Foodborne diseases are a series of diseases caused by people eating food contaminated by biological or chemical pathogenic factors. Foodborne diseases caused by food contamination seriously threaten people's physical health, becoming one of the most prominent public health problems in the world currently and also the biggest challenge faced by food safety.

[0003] Food packaging and preservation technology play a crucial role in effectively protecting food characteristics and food safety in the food supply chain. Food packaging can act as a barrier to protect food from physical damage such as collision and friction, can also reduce the impact of changes in surrounding environmental factors such as temperature, humidity, pH, oxygen, carbon dioxide, light, volatile substances, etc. on food, and can also block the invasion of pathogenic microorganisms into food. As a traditional food packaging and preservation material, PE material has some limitations: PE material is a non-degradable polymer material, bringing great pressure to the ecological environment; its antibacterial effect is limited, and it mainly plays a protective role through physical barrier. Therefore, it is necessary to develop a PE material with environmentally friendly antibacterial effect. Summary of the Invention

[0004] The purpose of the present invention is to provide an environmentally friendly antibacterial PE material and a preparation method thereof to solve the problems existing in the prior art.

[0005] An environmentally friendly antibacterial PE material and a preparation method thereof, the environmentally friendly antibacterial PE material is obtained by mixing and kneading and calendering polyethylene containing carboxyl and modified cellulose, and then performing chlorination treatment with sodium hypochlorite.

[0006] As an optimization, the polyethylene containing carboxyl is polymerized from ethylene and acrylic acid.

[0007] As an optimization, the modified cellulose is obtained by reacting oxidized cellulose with 3-amino-1,2,4-triazole;

[0008] The modified partial structure of the modified cellulose is as follows:

[0009]

[0010] Only represents one of the modified repeating units.

[0011] As an optimization, the oxidized cellulose is obtained by oxidizing cellulose with sodium periodate.

[0012] As an optimization, a preparation method of an environmentally friendly antibacterial PE material mainly includes the following preparation steps:

[0013] (1) Mix oxidized cellulose, 3-amino-1,2,4-triazole, absolute ethanol, and glacial acetic acid evenly according to a mass ratio of 1:1:6 - 8:3 - 4, stir and reflux at 65 - 75°C and 300 - 500 r / min for 20 - 24 h, cool to room temperature, then centrifuge and wash with absolute ethanol 3 - 5 times, and dry at 60 - 70°C and 50 - 100 Pa for 4 - 6 h to obtain modified cellulose;

[0014] (2) Mix acrylic acid and n-heptane evenly according to a mass ratio of 1:20 - 25, add them to a reaction kettle until it reaches 50% of the reaction kettle capacity, add a catalyst 0.03 - 0.05 times the mass of acrylic acid, seal the reaction kettle, heat up to 50 - 60°C, and introduce a hydrogen / ethylene mixed gas 3 - 5 times the volume of the reaction kettle at this temperature from the bottom of the reaction kettle to exhaust air. Close the outlet of the reaction kettle, continue to introduce the hydrogen / ethylene mixed gas until the pressure in the reaction kettle reaches 0.6 - 0.8 MPa. During the reaction process, introduce pure ethylene gas to keep the pressure in the reaction kettle constant, stir and react at 100 - 200 r / min for 20 - 24 h, cool to 10 - 20°C, filter and wash with pure water and absolute ethanol 3 - 5 times each, and dry at 60 - 70°C and 50 - 100 Pa for 4 - 6 h to obtain polyethylene containing carboxyl groups;

[0015] (3) Mix the polyethylene containing carboxyl groups and the modified cellulose evenly according to a mass ratio of 1:0.3 - 0.4, carry out plastic refining at 130 - 140°C for 40 - 50 min, then through the calendering method, calender and cool and solidify into a film with the required thickness, and carry out chlorination treatment on the film to obtain the environmentally friendly antibacterial PE material.

[0016] As an optimization, the preparation method of oxidized cellulose in step (1) is: under light-shielded conditions, mix cellulose, sodium periodate, and pure water evenly according to a mass ratio of 1:1 - 2:25 - 30, stir and react at 45 - 55°C and 300 - 500 r / min for 3 - 4 h, centrifuge and wash with pure water 3 - 5 times, and dry at 60 - 70°C and 50 - 100 Pa for 4 - 6 h to prepare it; the cellulose is powdered microcrystalline cellulose with a purity greater than 99.9%.

[0017] As an optimization, the catalyst in step (2) is a Ziegler-Natta catalyst.

[0018] As an optimization, the volume fraction of hydrogen in the hydrogen / ethylene mixed gas in step (2) is 5 - 10%.

[0019] As an optimization, the chlorination treatment method described in step (3) is as follows: Immerse the film in an aqueous sodium hypochlorite solution with a mass fraction of 8-10% and let it stand for 40-50 min, wash it with pure water 3-5 times, and dry it at 40-50 °C and 50-100 Pa for 4-6 h.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0021] When preparing the environmentally friendly antibacterial PE material of the present invention, acrylic acid is copolymerized during the ethylene polymerization process to obtain polyethylene containing carboxyl groups. After mixing and plasticizing and rolling the polyethylene containing carboxyl groups and the modified cellulose, it is then chlorinated with sodium hypochlorite to obtain the environmentally friendly antibacterial PE material.

[0022] First, oxidize cellulose with sodium periodate to obtain oxidized cellulose, and react the oxidized cellulose with 3-amino-1,2,4-triazole to obtain modified cellulose; a triazole Schiff base structure is formed on the modified cellulose, which has good antibacterial properties, and the triazole Schiff base structure on the modified cellulose is easily combined with the polyethylene containing carboxyl groups through hydrogen bonds or electrostatic forces to form a crosslinked structure, thereby improving the tensile strength.

[0023] Secondly, the raw materials of the present invention contain cellulose, which are widely sourced, green and environmentally friendly; chlorination treatment is carried out with sodium hypochlorite to convert the nitrogen-hydrogen bond on the triazole Schiff base structure of the modified cellulose into a nitrogen-chlorine bond, which has strong oxidizing properties, thereby improving the antibacterial performance. Specific embodiments

[0024] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0025] In order to more clearly illustrate the method provided by the present invention, it is described in detail through the following embodiments. The test methods for each index of the environmentally friendly antibacterial PE material prepared in the following embodiments are as follows:

[0026] Antibacterial performance: The antibacterial rate against Escherichia coli of the environmentally friendly antibacterial PE materials obtained in each embodiment and the products of the comparative examples is tested according to the QB / T 2591 standard.

[0027] Tensile performance: The tensile strength of the environmentally friendly antibacterial PE materials obtained in each embodiment and the products of the comparative examples is tested according to the GB / T 1040 standard.

[0028] Example 1

[0029] A preparation method of an environmentally friendly antibacterial PE material, the preparation method of the environmentally friendly antibacterial PE material mainly includes the following preparation steps:

[0030] (1) Under light-shielded conditions, cellulose, sodium periodate, and pure water are mixed evenly according to a mass ratio of 1:1:25, stirred and reacted at 45 °C and 300 r / min for 4 h, centrifuged and washed 3 times with pure water, and dried at 60 °C and 50 Pa for 6 h to obtain oxidized cellulose; oxidized cellulose, 3-amino-1,2,4-triazole, absolute ethanol, and glacial acetic acid are mixed evenly according to a mass ratio of 1:1:6:3, stirred and refluxed at 65 °C and 300 r / min for 24 h, cooled to room temperature, centrifuged and washed 3 times with absolute ethanol, and dried at 60 °C and 50 Pa for 6 h to obtain modified cellulose;

[0031] (2) Acrylic acid and n-heptane are mixed evenly according to a mass ratio of 1:20, added to a reaction kettle to reach 50% of the reaction kettle capacity, and a Ziegler-Natta catalyst 0.03 times the mass of acrylic acid is added. The reaction kettle is sealed, heated to 50 °C, and hydrogen / ethylene mixed gas 3 times the volume of the reaction kettle capacity at this temperature is introduced from the bottom of the reaction kettle to exhaust air. The volume fraction of hydrogen in the hydrogen / ethylene mixed gas is 5%. The outlet of the reaction kettle is closed, and the hydrogen / ethylene mixed gas is continuously introduced until the pressure of the reaction kettle reaches 0.6 MPa. During the reaction process, pure ethylene gas is introduced to keep the pressure in the reaction kettle constant, stirred and reacted at 100 r / min for 20 h, cooled to 10 °C, filtered and washed 3 times with pure water and absolute ethanol respectively, and dried at 60 °C and 50 Pa for 6 h to obtain polyethylene containing carboxyl groups;

[0032] (3) Polyethylene containing carboxyl groups and modified cellulose are mixed evenly according to a mass ratio of 1:0.3, plastified at 130 °C for 40 min, and then formed into a film with the required thickness by calendering method, calendered and cooled and solidified. The film is immersed in an 8% sodium hypochlorite aqueous solution and left standing for 50 min, washed 3 times with pure water, and dried at 40 °C and 50 Pa for 6 h to obtain the environmentally friendly antibacterial PE material.

[0033] Example 2

[0034] A preparation method of an environmentally friendly antibacterial PE material, the preparation method of the environmentally friendly antibacterial PE material mainly includes the following preparation steps:

[0035] (1) Under light - avoiding conditions, cellulose, sodium periodate, and pure water were mixed evenly at a mass ratio of 1:1.5:28, stirred and reacted at 50 °C and 400 r / min for 3.5 h, centrifuged and washed 4 times with pure water, and dried at 65 °C and 70 Pa for 4.5 h to obtain oxidized cellulose; oxidized cellulose, 3 - amino - 1,2,4 - triazole, absolute ethanol, and glacial acetic acid were mixed evenly at a mass ratio of 1:1:7:3.5, stirred and refluxed at 70 °C and 400 r / min for 22 h, cooled to room temperature, then centrifuged and washed 4 times with absolute ethanol, and dried at 65 °C and 70 Pa for 5 h to obtain modified cellulose;

[0036] (2) Acrylic acid and n - heptane were mixed evenly at a mass ratio of 1:22, added to a reaction kettle until it reached 50% of the reaction kettle capacity, and a Ziegler - Natta catalyst 0.04 times the mass of acrylic acid was added. The reaction kettle was sealed, heated to 55 °C, and hydrogen / ethylene mixed gas 4 times the volume of the reaction kettle capacity at this temperature was introduced from the bottom of the reaction kettle for air displacement. The volume fraction of hydrogen in the hydrogen / ethylene mixed gas was 7%. The outlet of the reaction kettle was closed, and the hydrogen / ethylene mixed gas was continuously introduced until the pressure in the reaction kettle reached 0.7 MPa. During the reaction process, pure ethylene gas was introduced to keep the pressure in the reaction kettle constant, stirred and reacted at 150 r / min for 22 h, cooled to 15 °C, filtered and washed 4 times with pure water and absolute ethanol respectively, and dried at 65 °C and 70 Pa for 5 h to obtain polyethylene containing carboxyl groups;

[0037] (3) Polyethylene containing carboxyl groups and modified cellulose were mixed evenly at a mass ratio of 1:0.35, plastified at 135 °C for 45 min, then formed into a film with the desired thickness by calendering method, the film was immersed in a 9% mass - fraction sodium hypochlorite aqueous solution and left standing for 45 min, washed 4 times with pure water, and dried at 45 °C and 70 Pa for 5 h to obtain an environmentally friendly antibacterial PE material.

[0038] Example 3

[0039] A preparation method of an environmentally friendly antibacterial PE material, the preparation method of the environmentally friendly antibacterial PE material mainly includes the following preparation steps:

[0040] (1) Under light - avoiding conditions, cellulose, sodium periodate, and pure water were mixed evenly at a mass ratio of 1:2:30, stirred and reacted at 50 °C and 500 r / min for 3 h, centrifuged and washed 5 times with pure water, and dried at 70 °C and 100 Pa for 4 h to obtain oxidized cellulose; oxidized cellulose, 3 - amino - 1,2,4 - triazole, absolute ethanol, and glacial acetic acid were mixed evenly at a mass ratio of 1:1:8:4, stirred and refluxed at 75 °C and 500 r / min for 20 h, cooled to room temperature, then centrifuged and washed 5 times with absolute ethanol, and dried at 70 °C and 100 Pa for 4 h to obtain modified cellulose;

[0041] (2) Mix acrylic acid and n-heptane evenly at a mass ratio of 1:25, add them to a reaction kettle until it reaches 50% of the reaction kettle capacity, and add a Ziegler-Natta catalyst with a mass 0.05 times that of acrylic acid. Seal the reaction kettle, heat it up to 60 °C, and introduce a hydrogen / ethylene mixed gas 5 times the capacity of the reaction kettle at this temperature from the bottom of the reaction kettle to expel air. The volume fraction of hydrogen in the hydrogen / ethylene mixed gas is 10%. Close the outlet of the reaction kettle, continue to introduce the hydrogen / ethylene mixed gas until the pressure of the reaction kettle reaches 0.8 MPa. During the reaction process, introduce pure ethylene gas to keep the pressure in the reaction kettle constant. Stir the reaction at 200 r / min for 20 h, cool it to 20 °C, filter it, and wash it 5 times with pure water and anhydrous ethanol respectively. Dry it at 70 °C and 100 Pa for 4 h to obtain polyethylene containing carboxyl groups;

[0042] (3) Mix the polyethylene containing carboxyl groups and the modified cellulose evenly at a mass ratio of 1:0.4, plastify it at 140 °C for 40 min, and then use the calendering method to calender and cool and solidify it into a film with the required thickness. Immerse the film in a 10% sodium hypochlorite aqueous solution and let it stand for 40 min, wash it 5 times with pure water, and dry it at 50 °C and 100 Pa for 4 h to obtain an environmentally friendly antibacterial PE material.

[0043] Comparative Example 1

[0044] A preparation method of an environmentally friendly antibacterial PE material, the preparation method of the environmentally friendly antibacterial PE material mainly includes the following preparation steps:

[0045] (1) Mix acrylic acid and n-heptane evenly at a mass ratio of 1:22, add them to a reaction kettle until it reaches 50% of the reaction kettle capacity, and add a Ziegler-Natta catalyst with a mass 0.04 times that of acrylic acid. Seal the reaction kettle, heat it up to 55 °C, and introduce a hydrogen / ethylene mixed gas 4 times the capacity of the reaction kettle at this temperature from the bottom of the reaction kettle to expel air. The volume fraction of hydrogen in the hydrogen / ethylene mixed gas is 7%. Close the outlet of the reaction kettle, continue to introduce the hydrogen / ethylene mixed gas until the pressure of the reaction kettle reaches 0.7 MPa. During the reaction process, introduce pure ethylene gas to keep the pressure in the reaction kettle constant. Stir the reaction at 150 r / min for 22 h, cool it to 15 °C, filter it, and wash it 4 times with pure water and anhydrous ethanol respectively. Dry it at 65 °C and 70 Pa for 5 h to obtain polyethylene containing carboxyl groups;

[0046] (2) Mix the carboxyl-containing polyethylene and cellulose evenly at a mass ratio of 1:0.35, plastify at 135 °C for 45 min, then by calendering, calender and cool and solidify into a film with the required thickness. Immerse the film in an aqueous sodium hypochlorite solution with a mass fraction of 9% and let it stand for 45 min, wash 4 times with pure water, and dry at 45 °C and 70 Pa for 5 h to obtain an environmentally friendly antibacterial PE material.

[0047] Comparative Example 2

[0048] A preparation method of an environmentally friendly antibacterial PE material, the preparation method of the environmentally friendly antibacterial PE material mainly includes the following preparation steps:

[0049] (1) Under light-shielded conditions, mix cellulose, sodium periodate, and pure water evenly at a mass ratio of 1:1.5:28, stir and react at 50 °C and 400 r / min for 3.5 h, centrifuge and wash 4 times with pure water, and dry at 65 °C and 70 Pa for 4.5 h to obtain oxidized cellulose; Mix oxidized cellulose, 3-amino-1,2,4-triazole, absolute ethanol, and glacial acetic acid evenly at a mass ratio of 1:1:7:3.5, stir and reflux at 70 °C and 400 r / min for 22 h, cool to room temperature, then centrifuge and wash 4 times with absolute ethanol, and dry at 65 °C and 70 Pa for 5 h to obtain modified cellulose;

[0050] (2) Add n-heptane to the reaction kettle until it reaches 50% of the reaction kettle capacity, and add a Ziegler-Natta catalyst with a mass 0.002 times that of n-heptane. Seal the reaction kettle, heat up to 55 °C, and introduce a hydrogen / ethylene mixed gas with a volume 4 times that of the reaction kettle capacity at this temperature from the bottom of the reaction kettle to exhaust air. The volume fraction of hydrogen in the hydrogen / ethylene mixed gas is 7%. Close the outlet of the reaction kettle, continue to introduce the hydrogen / ethylene mixed gas until the pressure in the reaction kettle reaches 0.7 MPa. During the reaction process, introduce pure ethylene gas to keep the pressure in the reaction kettle constant, stir and react at 150 r / min for 22 h, cool to 15 °C, filter and wash 4 times with pure water and absolute ethanol respectively, and dry at 65 °C and 70 Pa for 5 h to obtain polyethylene;

[0051] (3) Mix polyethylene and modified cellulose evenly at a mass ratio of 1:0.35, plastify at 135 °C for 45 min, then by calendering, calender and cool and solidify into a film with the required thickness. Immerse the film in an aqueous sodium hypochlorite solution with a mass fraction of 9% and let it stand for 45 min, wash 4 times with pure water, and dry at 45 °C and 70 Pa for 5 h to obtain an environmentally friendly antibacterial PE material.

[0052] Comparative Example 3

[0053] A preparation method of an environmentally friendly antibacterial PE material, the preparation method of the environmentally friendly antibacterial PE material mainly includes the following preparation steps:

[0054] (1) Under light - avoiding conditions, cellulose, sodium periodate, and pure water were mixed evenly at a mass ratio of 1:1.5:28, stirred and reacted at 50 °C and 400 r / min for 3.5 h, centrifuged and washed 4 times with pure water, and dried at 65 °C and 70 Pa for 4.5 h to obtain oxidized cellulose; oxidized cellulose, 3 - amino - 1,2,4 - triazole, absolute ethanol, and glacial acetic acid were mixed evenly at a mass ratio of 1:1:7:3.5, stirred and refluxed at 70 °C and 400 r / min for 22 h, cooled to room temperature, then centrifuged and washed 4 times with absolute ethanol, and dried at 65 °C and 70 Pa for 5 h to obtain modified cellulose;

[0055] (2) Acrylic acid and n - heptane were mixed evenly at a mass ratio of 1:22, added to a reaction kettle until it reached 50% of the reaction kettle capacity, and a Ziegler - Natta catalyst 0.04 times the mass of acrylic acid was added. The reaction kettle was sealed, heated to 55 °C, and hydrogen / ethylene mixed gas 4 times the volume of the reaction kettle capacity at this temperature was introduced from the bottom of the reaction kettle for air displacement. The volume fraction of hydrogen in the hydrogen / ethylene mixed gas was 7%. The outlet of the reaction kettle was closed, and the hydrogen / ethylene mixed gas was continuously introduced until the pressure in the reaction kettle reached 0.7 MPa. During the reaction process, pure ethylene gas was introduced to keep the pressure in the reaction kettle constant, stirred and reacted at 150 r / min for 22 h, cooled to 15 °C, filtered and washed 4 times each with pure water and absolute ethanol, and dried at 65 °C and 70 Pa for 5 h to obtain poly(ethylene) containing carboxyl groups;

[0056] (3) Poly(ethylene) containing carboxyl groups and modified cellulose were mixed evenly at a mass ratio of 1:0.35, plastified at 135 °C for 45 min, then formed into a film with the desired thickness by calendering, cooled and solidified, washed 4 times with pure water, and dried at 45 °C and 70 Pa for 5 h to obtain an environmentally friendly antibacterial PE material.

[0057] Effect Example

[0058] The following Table 1 gives the performance analysis results of the antibacterial and formaldehyde - removing properties of the environmentally friendly antibacterial PE materials prepared in Examples 1 - 3 and Comparative Examples 1 - 3 of the present invention.

[0059] Table 1

[0060] Antibacterial rate Tensile strength Antibacterial rate Tensile strength Example 1 99.3％ 29.4 MPa Comparative Example 1 73.5％ 24.1 MPa Example 2 99.3％ 29.6 MPa Comparative Example 2 99.2％ 24.4 MPa Example 3 99.1％ 29.3 MPa Comparative Example 3 91.6％ 29.8 MPa

[0061] From the comparison of the experimental data of Examples 1 - 3 and Comparative Examples 1 - 3 in Table 2, it can be found that the environmentally friendly antibacterial PE material prepared by the present invention has good antibacterial performance and tensile properties.

[0062] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1, it can be found that the antibacterial rate and tensile strength of Examples 1, 2, 3 are higher than those of Comparative Example 1, indicating that the cellulose is modified, and a triazole Schiff base structure is formed on the modified cellulose, which has good antibacterial properties. Moreover, the triazole Schiff base structure on the modified cellulose is easily combined with carboxyl-containing polyethylene through hydrogen bonds or electrostatic interaction to form a cross-linked structure, thereby improving the tensile strength. From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2, it can be found that the tensile strength of Examples 1, 2, 3 is higher than that of Comparative Example 2, indicating that acrylic acid is copolymerized during the ethylene polymerization process to obtain carboxyl-containing polyethylene, and the carboxyl groups on the carboxyl-containing polyethylene are easily combined with the triazole Schiff base structure on the modified cellulose through hydrogen bonds or electrostatic interaction to form a cross-linked structure, thereby improving the tensile strength. From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found that the antibacterial rate of Examples 1, 2, 3 is higher than that of Comparative Example 3, indicating that chlorination treatment with sodium hypochlorite converts the nitrogen-hydrogen bond on the triazole Schiff base structure of the modified cellulose into a nitrogen-chlorine bond, which has strong oxidizing properties, thereby improving the antibacterial performance.

[0063] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claimed claim.

Claims

1. An environmentally friendly antibacterial PE material, characterized in that, The environmentally friendly antibacterial PE material is prepared by mixing polyethylene containing carboxyl groups and modified cellulose, subjecting the mixture to plastic refining and calendering, and then performing chlorination treatment with sodium hypochlorite; The polyethylene containing carboxyl groups is polymerized from ethylene and acrylic acid; The modified cellulose is prepared by reacting oxidized cellulose with 3-amino-1,2,4-triazole; The modified structure of the modified cellulose is as follows: Only one of the modified repeating units is shown; The preparation method of the environmentally friendly antibacterial PE material mainly includes the following preparation steps: Mix polyethylene containing carboxyl groups and modified cellulose evenly according to a mass ratio of 1:0.3 - 0.4, perform plastic refining at 130 - 140 °C for 40 - 50 min, then through the calendering method, calender and cool and solidify into a film with the required thickness, and perform chlorination treatment on the film to obtain the environmentally friendly antibacterial PE material.

2. The environmentally friendly antibacterial PE material according to claim 1, characterized in that, The oxidized cellulose is prepared by oxidizing cellulose with sodium periodate.

3. An environmentally friendly antibacterial PE material according to claim 1, characterized in that, The preparation method of oxidized cellulose is as follows: Under light-shielded conditions, mix cellulose, sodium periodate, and pure water evenly according to a mass ratio of 1:1 - 2:25 - 30, stir and react at 45 - 55 °C and 300 - 500 r / min for 3 - 4 h, perform centrifugal separation and wash with pure water 3 - 5 times, and dry at 60 - 70 °C and 50 - 100 Pa for 4 - 6 h to prepare it; the cellulose is powdered microcrystalline cellulose with a purity greater than 99.9%.

4. An environmentally friendly antibacterial PE material according to claim 1, characterized in that, The method of chlorination treatment is as follows: Immerse the film in an aqueous solution of sodium hypochlorite with a mass fraction of 8 - 10% and let it stand for 40 - 50 min, wash with pure water 3 - 5 times, and dry at 40 - 50 °C and 50 - 100 Pa for 4 - 6 h.

5. An environment-friendly antibacterial PE material according to claim 1, characterized in that, The preparation method of the polyethylene containing carboxyl groups is as follows: Mix acrylic acid and n-heptane evenly according to a mass ratio of 1:20 - 25, add them to the reaction kettle until it reaches 50% of the reaction kettle capacity, add a catalyst with a mass 0.03 - 0.05 times that of acrylic acid, seal the reaction kettle, heat up to 50 - 60 °C and introduce a hydrogen / ethylene mixed gas with a volume 3 - 5 times that of the reaction kettle capacity at this temperature from the bottom of the reaction kettle to exhaust air, close the outlet of the reaction kettle, continue to introduce the hydrogen / ethylene mixed gas until the pressure in the reaction kettle reaches 0.6 - 0.8 MPa, introduce pure ethylene gas during the reaction to keep the pressure in the reaction kettle constant, stir and react at 100 - 200 r / min for 20 - 24 h, cool to 10 - 20 °C, filter and wash with pure water and anhydrous ethanol 3 - 5 times each, and dry at 60 - 70 °C and 50 - 100 Pa for 4 - 6 h to obtain the polyethylene containing carboxyl groups.

6. The environmentally friendly antibacterial PE material according to claim 1, characterized in that, The preparation method of the modified cellulose is as follows: Mix oxidized cellulose, 3-amino-1,2,4-triazole, anhydrous ethanol, and glacial acetic acid evenly according to a mass ratio of 1:1:6 - 8:3 - 4, stir and reflux at 65 - 75 °C and 300 - 500 r / min for 20 - 24 h, cool to room temperature, perform centrifugal separation and wash with anhydrous ethanol 3 - 5 times, and dry at 60 - 70 °C and 50 - 100 Pa for 4 - 6 h to obtain the modified cellulose.

7. An environmentally friendly antibacterial PE material according to claim 5, characterized in that, The catalyst is a Ziegler-Natta catalyst.

8. An environmentally friendly antibacterial PE material according to claim 5, characterized in that, The volume fraction of hydrogen in the hydrogen / ethylene mixed gas is 5 to 10%.

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