Antibacterial medical packaging material and method for preparing the same

Abstract

The application discloses an antibacterial medical packaging material and a preparation method thereof, and relates to the packaging material field. When the antibacterial medical packaging material is prepared, chitosan and N-methylcarbazole-3,6-dialdehyde are reacted to obtain chitosan microspheres; then the chitosan microspheres are sequentially reacted with 2-mercapto-S-thiobenzoyl acetic acid and allyl trimethyl ammonium chloride to obtain modified chitosan microspheres; polylactic acid is reacted with 2-aminoethyl hypophosphorous acid to obtain modified polylactic acid; and the modified chitosan microspheres and the modified polylactic acid are uniformly mixed and then extruded into a film to obtain the antibacterial medical packaging material. The antibacterial medical packaging material prepared by the application has excellent flame retardance, antibacterial property and mechanical property.

Description

Technical Field

[0001] This invention relates to the field of packaging materials, specifically to an antibacterial medical packaging material and its preparation method. Background Technology

[0002] Functional materials used in the preparation of medical protective and packaging products must possess certain mechanical properties, microbial barrier properties, adaptability to various sterilization methods, waterproofness, breathability, and chemical corrosion resistance. Materials used in medical packaging, in particular, must possess excellent clean-peel properties to prevent short fibers and dust generated during packaging tearing from contaminating the medical devices and hygiene products inside. Traditional medical packaging materials such as gauze and cotton cloth have excellent breathability and a soft texture, making them commonly used medical packaging materials. However, the loose structure resulting from repeated use reduces their microbial barrier capacity, leading to a short sterile packaging shelf life and failing to meet the requirements for medium- to long-term sterile packaging. Therefore, this invention prepares a medical packaging material with excellent antibacterial properties. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial medical packaging material and its preparation method, so as to solve the problems existing in the prior art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0005] An antibacterial medical packaging material is obtained by extruding a mixture of modified chitosan microspheres and modified polylactic acid into a film.

[0006] As an optimization, the modified polylactic acid is obtained by reacting polylactic acid with 2-aminoethyl hypophosphite.

[0007] As an optimization, the polylactic acid is sourced from Hubei Xinghengye Technology Co., Ltd.

[0008] As an optimization, the modified chitosan microspheres are obtained by reacting chitosan microspheres sequentially with 2-mercapto-S-thiobenzoylacetic acid and allyltrimethylammonium chloride.

[0009] As an optimization, the chitosan microspheres are obtained by reacting chitosan with N-methylcarbazole-3,6-dialdehyde.

[0010] As an optimization, the chitosan was sourced from Wuhan Shuer Biotechnology Co., Ltd.

[0011] A method for preparing an antibacterial medical packaging material includes the following preparation steps:

[0012] (1) Chitosan and acetic acid solution with a mass fraction of 2%~4% were mixed at a mass ratio of 1:(98~100) and stirred at 450~550rpm for 11~13h to obtain an aqueous phase; Span80 and liquid paraffin were mixed at a mass ratio of 1:(11~13) to obtain an oil phase; 0.05~0.15 times the volume of the aqueous phase was added to the oil phase at 45~55℃ and 450~550rpm, and emulsified for 3~5h. Then, 0.003~0.005 times the volume of the N-methylcarbazole-3,6-dialdehyde was added and stirred for another 3~5h. After cooling to room temperature, the mixture was centrifuged and washed 3~5 times with petroleum ether and isopropanol, respectively. The mixture was then dried at 55~65℃ for 11~13h to obtain chitosan microspheres.

[0013] (2) Mix allyltrimethylammonium chloride, anhydrous ethanol, and deionized water at a mass ratio of 1:(2~4):(2~4) to obtain a modified solution; immerse chitosan microspheres in 0.2~0.4mol / L N,N'-carbonyldiimidazolium dimethyl sulfoxide solution, and sonicate at 35~45℃ in the dark for 1~3h. Add 1.5~1.7 times the mass of chitosan microspheres of 2-mercapto-S-thiobenzoylacetic acid, continue sonicating for 1~3h, filter, and wash 3~5 times with dimethyl sulfoxide and anhydrous ethanol respectively. Pre-modified chitosan microspheres were obtained by drying at 30-40℃ for 23-25 ​​hours. The pre-modified chitosan microspheres, ammonium persulfate, tetramethylethylenediamine and the modification solution were mixed at a mass ratio of 1:(0.01-0.02):(0.01-0.02):(25-35). The mixture was stirred at 25-35℃ and 100-300 rpm for 11-13 hours, then filtered. The microspheres were washed 3-5 times with N,N-dimethylformamide and anhydrous ethanol, respectively, and dried at 45-55℃ for 6-8 hours to obtain modified chitosan microspheres.

[0014] (3) Mix polylactic acid, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide and dimethyl sulfoxide in a mass ratio of 1:(0.3~0.5):(0.2~0.3):(18~20), add 1~2 times the mass of polylactic acid and 2-aminoethyl hypophosphoric acid at 80~90℃, continue stirring for 11~13h, extract with dichloromethane 2~4 times, precipitate with ice-cold diethyl ether and filter to obtain modified polylactic acid;

[0015] (4) The modified polylactic acid and modified chitosan microspheres are mixed at a mass ratio of 1:(0.04~0.06) and extruded into a film with a thickness of 50~60µm using a single screw extruder under the following conditions: zone 1 temperature 150~160℃, zone 2 temperature 155~165℃, zone 3 temperature 165~175℃, zone 4 temperature 170~180℃, zone 5 temperature 165~175℃, zone 6 temperature 165~175℃, zone 7 temperature 165~175℃, die head temperature 180~190℃, feed device speed 3~5r / min, screw speed 45~55r / min. The film is then left to stand at 60~70℃ for 7~9h to obtain antibacterial medical packaging material.

[0016] As an optimization, the reaction equation for the chitosan microspheres in step (1) is:

[0017] .

[0018] As an optimization, the reaction equation for the modified chitosan microspheres in step (2) is:

[0019] .

[0020] As an optimization, the reaction equation for the modified polylactic acid in step (3) is as follows:

[0021] .

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] In preparing antibacterial medical packaging materials, this invention involves reacting chitosan and N-methylcarbazole-3,6-dialdehyde to obtain chitosan microspheres; then reacting the chitosan microspheres sequentially with 2-mercapto-S-thiobenzoylacetic acid and allyltrimethylammonium chloride to obtain modified chitosan microspheres; reacting polylactic acid and 2-aminoethyl hypophosphite to obtain modified polylactic acid; and finally mixing the modified chitosan microspheres and modified polylactic acid and extruding them into a film to obtain the antibacterial medical packaging material.

[0024] First, chitosan and N-methylcarbazole-3,6-dialdehyde were reacted to obtain chitosan microspheres. Then, the chitosan microspheres were sequentially reacted with 2-mercapto-S-thiobenzoylacetic acid and allyltrimethylammonium chloride to obtain modified chitosan microspheres. Chitosan was cross-linked with N-methylcarbazole-3,6-dialdehyde via a Schiff base reaction to form microspheres, introducing a carbazole structure, which disrupts bacterial cell membranes and improves the antibacterial properties of the medical packaging material. Simultaneously, the Schiff base bonds on the chitosan microspheres can be added via phosphorus-hydrogen bonds, forming a stable chemical bond, preventing the chitosan microspheres from slipping and detaching, and improving the long-lasting antibacterial properties of the medical packaging material. Finally, allyltrimethylammonium chloride was grafted onto the chitosan microspheres using chain transfer polymerization to form a stable long-chain quaternary ammonium polymer, which interrupts cell metabolism and improves the antibacterial properties of the medical packaging material.

[0025] Secondly, polylactic acid (PLA) and 2-aminoethyl hypophosphite are reacted to obtain modified PLA; modified chitosan microspheres and modified PLA are mixed and extruded into a film to obtain antibacterial medical packaging material; 2-aminoethyl hypophosphite is grafted onto PLA through the reaction of amino and carboxyl groups, introducing phosphorus to capture free radicals and interrupt the chain reaction, thereby improving the flame retardancy of the medical packaging material; at the same time, the phosphorus-hydrogen bonds on 2-aminoethyl hypophosphite can add to the carbon-nitrogen double bonds on chitosan microspheres, forming a cross-linking network with chitosan microspheres as cross-linking sites, thereby improving the mechanical properties of the medical packaging material. Attached Figure Description

[0026] Figure 1 This is a SEM image of the modified chitosan microspheres.

[0027] Figure 2 Here is the FTIR image of the modified chitosan microspheres, where:

[0028] 2888cm -1 —The CH stretching vibration of saturated hydrocarbon groups;

[0029] 1768cm -1 —Stretching vibration of the carbonyl group;

[0030] 1344cm -1 1470cm -1 —The CH bending vibration of saturated hydrocarbon groups;

[0031] 1110cm -1 —Stretching vibrations of the ether bond;

[0032] 843cm -1 963cm -1 —Out-of-plane bending vibration of the benzene ring.

[0033] Figure 3 Here is the FTIR spectrum of modified polylactic acid, where:

[0034] 4000~2500cm⁻¹ — Stretching vibration of CH bond;

[0035] 2500~1500cm⁻¹ — Stretching vibration of the carbonyl group;

[0036] 1500~650cm-1 — Stretching vibration of ether bond. Detailed Implementation

[0037] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0038] The raw materials used in the following examples and comparative examples are all commercially available:

[0039] The polylactic acid was sourced from Hubei Xinghengye Technology Co., Ltd.

[0040] The chitosan was obtained from Wuhan Shuer Biotechnology Co., Ltd.

[0041] Example 1: A method for preparing an antibacterial medical packaging material, the method comprising the following steps:

[0042] (1) Chitosan and acetic acid solution with a mass fraction of 2% were mixed at a mass ratio of 1:98 and stirred at 450 rpm for 13 h to obtain an aqueous phase; Span80 and liquid paraffin were mixed at a mass ratio of 1:11 to obtain an oil phase; at 45℃ and 450 rpm, 0.05 times the volume of the aqueous phase was added to the oil phase at a uniform speed, and emulsified for 5 h. Then, 0.003 times the volume of the oil phase of N-methylcarbazole-3,6-dialdehyde was added and stirred for another 5 h. After cooling to room temperature, the mixture was centrifuged and washed three times with petroleum ether and isopropanol, respectively. The mixture was then dried at 55℃ for 13 h to obtain chitosan microspheres.

[0043] (2) Allyltrimethylammonium chloride, anhydrous ethanol and deionized water were mixed in a mass ratio of 1:2:2 to obtain a modified solution; chitosan microspheres were immersed in 0.2 mol / L N,N'-carbonyldiimidazolium dimethyl sulfoxide solution and sonicated at 35°C in the dark for 3 h; 1.5 times the mass of chitosan microspheres of 2-mercapto-S-thiobenzoylacetic acid was added, and sonication was continued for 3 h. After filtration, the microspheres were washed three times with dimethyl sulfoxide and anhydrous ethanol, and dried at 30°C for 25 h to obtain pre-modified chitosan microspheres; the pre-modified chitosan microspheres, ammonium persulfate, tetramethylethylenediamine and the modified solution were mixed in a mass ratio of 1:0.01:0.01:25 and stirred at 25°C and 100 rpm for 13 h. After filtration, the microspheres were washed three times with N,N-dimethylformamide and anhydrous ethanol, and dried at 45°C for 8 h to obtain modified chitosan microspheres.

[0044] (3) Polylactic acid, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide and dimethyl sulfoxide were mixed in a mass ratio of 1:0.3:0.2:18. At 80°C, 2-aminoethyl hypophosphoric acid with a mass equal to that of polylactic acid was added. The mixture was stirred for 13 h. The mixture was extracted twice with dichloromethane, precipitated with ice-cold diethyl ether, and then filtered to obtain modified polylactic acid.

[0045] (4) The modified polylactic acid and modified chitosan microspheres were mixed at a mass ratio of 1:0.04 and extruded into a film with a thickness of 50µm using a single screw extruder under the following conditions: zone 1 temperature 150℃, zone 2 temperature 155℃, zone 3 temperature 165℃, zone 4 temperature 170℃, zone 5 temperature 165℃, zone 6 temperature 165℃, zone 7 temperature 165℃, die head temperature 180℃, feed device speed 3r / min, and screw speed 45r / min. The film was then left to stand at 60℃ for 9h to obtain antibacterial medical packaging material.

[0046] Example 2: A method for preparing an antibacterial medical packaging material, the method comprising the following steps:

[0047] (1) Chitosan and acetic acid solution with a mass fraction of 3% were mixed at a mass ratio of 1:99 and stirred at 500 rpm for 12 h to obtain an aqueous phase; Span80 and liquid paraffin were mixed at a mass ratio of 1:12 to obtain an oil phase; at 50℃ and 500 rpm, 0.1 times the volume of the aqueous phase was added to the oil phase at a uniform speed, and emulsified for 4 h. Then, 0.004 times the volume of the oil phase of N-methylcarbazole-3,6-dialdehyde was added and stirred for another 4 h. After cooling to room temperature, the mixture was centrifuged and washed 4 times with petroleum ether and isopropanol, respectively. The mixture was then dried at 60℃ for 12 h to obtain chitosan microspheres.

[0048] (2) Allyltrimethylammonium chloride, anhydrous ethanol and deionized water were mixed in a mass ratio of 1:3:3 to obtain a modified solution; chitosan microspheres were immersed in 0.3 mol / L N,N'-carbonyldiimidazolium dimethyl sulfoxide solution and sonicated at 40°C in the dark for 2 h. 1.6 times the mass of chitosan microspheres of 2-mercapto-S-thiobenzoylacetic acid was added and sonicated for another 2 h. After filtration, the microspheres were washed 4 times with dimethyl sulfoxide and anhydrous ethanol, and dried at 35°C for 24 h to obtain pre-modified chitosan microspheres; the pre-modified chitosan microspheres, ammonium persulfate, tetramethylethylenediamine and the modified solution were mixed in a mass ratio of 1:0.015:0.015:30 and stirred at 30°C and 200 rpm for 12 h. After filtration, the microspheres were washed 4 times with N,N-dimethylformamide and anhydrous ethanol, and dried at 50°C for 7 h to obtain modified chitosan microspheres.

[0049] (3) Polylactic acid, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide and dimethyl sulfoxide were mixed in a mass ratio of 1:0.4:0.25:19. At 85°C, 2-aminoethyl hypophosphoric acid with a mass of 1.5 times that of polylactic acid was added. The mixture was stirred for 12 h. The mixture was extracted three times with dichloromethane. After precipitation with ice-cold diethyl ether, the mixture was filtered to obtain modified polylactic acid.

[0050] (4) The modified polylactic acid and modified chitosan microspheres were mixed at a mass ratio of 1:0.05 and extruded into a film with a thickness of 55µm using a single screw extruder under the following conditions: zone 1 temperature 155℃, zone 2 temperature 160℃, zone 3 temperature 170℃, zone 4 temperature 175℃, zone 5 temperature 170℃, zone 6 temperature 170℃, zone 7 temperature 170℃, die head temperature 185℃, feed device speed 4r / min, and screw speed 50r / min. The film was then left to stand at 65℃ for 8 hours to obtain antibacterial medical packaging material.

[0051] Example 3: A method for preparing an antibacterial medical packaging material, the method comprising the following steps:

[0052] (1) Chitosan and acetic acid solution with a mass fraction of 4% were mixed at a mass ratio of 1:100 and stirred at 550 rpm for 11 h to obtain an aqueous phase; Span80 and liquid paraffin were mixed at a mass ratio of 1:13 to obtain an oil phase; at 55℃ and 550 rpm, 0.15 times the volume of the aqueous phase was added to the oil phase at a uniform speed, and emulsified for 3 h. Then, 0.005 times the volume of the oil phase of N-methylcarbazole-3,6-dialdehyde was added and stirred for another 3 h. After cooling to room temperature, the mixture was centrifuged and washed 5 times with petroleum ether and isopropanol, respectively. The mixture was then dried at 65℃ for 11 h to obtain chitosan microspheres.

[0053] (2) Allyltrimethylammonium chloride, anhydrous ethanol and deionized water were mixed in a mass ratio of 1:4:4 to obtain a modified solution; chitosan microspheres were immersed in 0.4 mol / L N,N'-carbonyldiimidazolium dimethyl sulfoxide solution and sonicated at 45°C in the dark for 1 h. 1.7 times the mass of chitosan microspheres of 2-mercapto-S-thiobenzoylacetic acid was added and sonicated for another 3 h. After filtration, the microspheres were washed 5 times with dimethyl sulfoxide and anhydrous ethanol respectively and dried at 40°C for 23 h to obtain pre-modified chitosan microspheres; the pre-modified chitosan microspheres, ammonium persulfate, tetramethylethylenediamine and the modified solution were mixed in a mass ratio of 1:0.02:0.02:35 and stirred at 35°C and 300 rpm for 11 h. After filtration, the microspheres were washed 5 times with N,N-dimethylformamide and anhydrous ethanol respectively and dried at 55°C for 6 h to obtain modified chitosan microspheres;

[0054] (3) Mix polylactic acid, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide and dimethyl sulfoxide in a mass ratio of 1:0.5:0.3:20. Add 2-aminoethyl hypophosphoric acid at 90°C with twice the mass of polylactic acid and continue stirring for 11 h. Extract with dichloromethane 4 times, precipitate with ice-cold diethyl ether and filter to obtain modified polylactic acid.

[0055] (4) The modified polylactic acid and modified chitosan microspheres were mixed at a mass ratio of 1:0.06 and extruded into a film with a thickness of 60µm using a single screw extruder under the following conditions: zone 1 temperature 160℃, zone 2 temperature 165℃, zone 3 temperature 175℃, zone 4 temperature 180℃, zone 5 temperature 175℃, zone 6 temperature 175℃, zone 7 temperature 175℃, die head temperature 190℃, feed device speed 5r / min, and screw speed 55r / min. The film was then left to stand at 70℃ for 7h to obtain antibacterial medical packaging material.

[0056] Comparative Example 1: The preparation method of the antibacterial medical packaging material in Comparative Example 1 differs from that in Example 2 only in step (1). Step (1) is modified as follows: Chitosan and a 3% acetic acid solution are mixed at a mass ratio of 1:99 and stirred at 500 rpm for 12 h to obtain an aqueous phase; Span80 and liquid paraffin are mixed at a mass ratio of 1:12 to obtain an oil phase; at 50°C and 500 rpm, 0.1 times the volume of the aqueous phase is added to the oil phase at a uniform rate, emulsified for 4 h, and then 0.004 times the volume of the hexamethylenetetramine is added, and stirring is continued for 4 h. After cooling to room temperature, the mixture is centrifuged, washed four times with petroleum ether and isopropanol respectively, and dried at 60°C for 12 h to obtain chitosan microspheres. The remaining steps are the same as in Example 2.

[0057] Comparative Example 2: The preparation method of the antibacterial medical packaging material in Comparative Example 2 differs from that in Example 2 only in step (2), which is omitted. The remaining steps are the same as in Example 2.

[0058] Comparative Example 3: The preparation method of the antibacterial medical packaging material in Comparative Example 3 differs from that in Example 2 only in step (3), which is omitted. The remaining steps are the same as in Example 2.

[0059] Test Example 1: Flame Retardancy

[0060] Test method: The antibacterial medical packaging materials obtained from each example and comparative example were cut into samples of 100×10×0.4mm in size, and the limiting oxygen index was tested.

[0061] Table 1

[0062] .

[0063] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-3 in Table 1 reveals that the antibacterial medical packaging material prepared by this invention has good flame retardancy.

[0064] Comparative Example 3 was not grafted with 2-aminoethyl hypophosphite. By comparison, Examples 1, 2, and 3 showed a higher limiting oxygen index than Comparative Example 3, indicating that grafting 2-aminoethyl hypophosphite onto polylactic acid through the reaction of amino and carboxyl groups introduces phosphorus to capture free radicals, interrupt the chain reaction, and improve the flame retardancy of medical packaging materials.

[0065] Test Example 2: Antibacterial Properties

[0066] Test method: The antibacterial medical packaging materials obtained in each example and comparative example were rinsed with deionized water for 1 min and then dried at 65°C. The rinsing and drying were repeated 10 times before sterilization. The materials were then cut into small round pieces with a diameter of 1.2 cm. Escherichia coli was transferred from a low-temperature storage state to room temperature conditions for recovery and cultured in LB medium with shaking for 11 h until the bacterial concentration reached 10. 8 Cells / mL, 100 μL of the cultured bacterial solution was taken and evenly spread on the surface of the agar medium. Small discs were placed in the center of the medium with the bacterial solution, and the medium with the small discs was placed in a 37°C incubator for 12 h. Optical photographs of the agar medium removed from the incubator were taken with a digital camera, and the diameter of the inhibition zone was determined using ImageJ software.

[0067] Table 2

[0068] .

[0069] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-3 in Table 2 reveals that the antibacterial medical packaging material prepared by the present invention has good antibacterial properties.

[0070] Comparative Example 1 did not use N-methylcarbazole-3,6-dialdehyde crosslinking. By comparison, the diameter of the inhibition zone of Examples 1, 2, and 3 was larger than that of Comparative Example 1, indicating that the formation of microspheres by crosslinking chitosan with N-methylcarbazole-3,6-dialdehyde through Schiff base reaction introduces a carbazole structure, which disrupts the bacterial cell membrane and improves the antibacterial properties of medical packaging materials.

[0071] Comparative Example 2 was not grafted with allyltrimethylammonium chloride. By comparison, the diameter of the inhibition zone of Examples 1, 2, and 3 was larger than that of Comparative Example 2, indicating that the grafting of allyltrimethylammonium chloride onto chitosan microspheres by chain transfer polymerization forms a stable long-chain quaternary ammonium polymer, which interrupts cell metabolism and improves the antibacterial properties of medical packaging materials.

[0072] Comparative Example 3 was not grafted with 2-aminoethyl hypophosphite. By comparison, the diameter of the inhibition zone of Comparative Example 3 was larger than that of Examples 1, 2, and 3, indicating that the formation of microspheres by cross-linking chitosan with N-methylcarbazole-3,6-dialdehyde through Schiff base reaction allows the Schiff base bonds on the chitosan microspheres to be added by phosphorus-hydrogen bonds, forming a stable chemical bond, preventing the chitosan microspheres from slipping off, and improving the durable antibacterial properties of medical packaging materials.

[0073] Test Example 3: Mechanical Properties

[0074] Test method: The antibacterial medical packaging materials obtained from each embodiment and comparative example were tested for tensile strength using a universal tensile testing machine in accordance with GB / T1040.

[0075] Table 3

[0076] .

[0077] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-3 in Table 3 reveals that the antibacterial medical packaging material prepared by this invention has good mechanical properties.

[0078] Comparative Example 3 was not grafted with 2-aminoethyl hypophosphite. By comparison, Examples 1, 2, and 3 showed higher tensile strength than Comparative Example 3, indicating that grafting 2-aminoethyl hypophosphite onto polylactic acid via the reaction of amino and carboxyl groups allows the phosphorus-hydrogen bonds on 2-aminoethyl hypophosphite to add to the carbon-nitrogen double bonds on chitosan microspheres. Using chitosan microspheres as crosslinking sites, a crosslinking network is formed, improving the mechanical properties of medical packaging materials.

[0079] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an antibacterial medical packaging material, characterized in that, The preparation steps include the following: (1) Chitosan and acetic acid solution with a mass fraction of 2%~4% were mixed at a mass ratio of 1:(98~100) and stirred at 450~550rpm for 11~13h to obtain an aqueous phase; at 45~55℃ and 450~550rpm, 0.05~0.15 times the volume of the aqueous phase of the oil phase were added to the oil phase at a uniform speed, and emulsified for 3~5h. Then, 0.003~0.005 times the volume of the oil phase of N-methylcarbazole-3,6-dialdehyde was added and stirred for another 3~5h. After cooling to room temperature, the mixture was centrifuged and washed 3~5 times with petroleum ether and isopropanol, respectively. The mixture was then dried at 55~65℃ for 11~13h to obtain chitosan microspheres. (2) Immerse chitosan microspheres in 0.2-0.4 mol / L N,N'-carbonyldiimidazolium dimethyl sulfoxide solution, sonicate at 35-45℃ in the dark for 1-3 h, add 1.5-1.7 times the mass of chitosan microspheres of 2-mercapto-S-thiobenzoylacetic acid, continue sonication for 1-3 h, filter, wash with dimethyl sulfoxide and anhydrous ethanol 3-5 times respectively, and dry at 30-40℃ for 23-25 ​​h to obtain pre-modified chitosan microspheres; add allyltrimethylammonium chloride, anhydrous ethanol and deionized water... Water was mixed at a mass ratio of 1:(2~4):(2~4) to obtain a modified solution; the pre-modified chitosan microspheres, ammonium persulfate, tetramethylethylenediamine and the modified solution were mixed at a mass ratio of 1:(0.01~0.02):(0.01~0.02):(25~35), stirred at 25~35℃ and 100~300rpm for 11~13h, filtered, washed 3~5 times with N,N-dimethylformamide and anhydrous ethanol respectively, and dried at 45~55℃ for 6~8h to obtain modified chitosan microspheres; (3) Mix polylactic acid, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide and dimethyl sulfoxide in a mass ratio of 1:(0.3~0.5):(0.2~0.3):(18~20), add 1~2 times the mass of polylactic acid and 2-aminoethyl hypophosphoric acid at 80~90℃, continue stirring for 11~13h, extract with dichloromethane 2~4 times, precipitate with ice-cold diethyl ether and filter to obtain modified polylactic acid; (4) Mix the modified polylactic acid and modified chitosan microspheres at a mass ratio of 1:(0.04~0.06), extrude them into a film with a thickness of 50~60µm using a single screw extruder, and let it stand at 60~70℃ for 7~9h to obtain antibacterial medical packaging material.

2. The method for preparing an antibacterial medical packaging material according to claim 1, characterized in that, The preparation process of the oil phase in step (1) is as follows: Span80 and liquid paraffin are mixed at a mass ratio of 1:(11~13) to obtain the oil phase.

3. The method for preparing an antibacterial medical packaging material according to claim 1, characterized in that, The process parameters for extruding film using a single screw extruder in step (4) are as follows: Zone 1 temperature 150~160℃, Zone 2 temperature 155~165℃, Zone 3 temperature 165~175℃, Zone 4 temperature 170~180℃, Zone 5 temperature 165~175℃, Zone 6 temperature 165~175℃, Zone 7 temperature 165~175℃, Die head temperature 180~190℃, Feeding device speed 3~5r / min, Screw speed 45~55r / min.

4. An antibacterial medical packaging material prepared by the method of preparing antibacterial medical packaging material according to any one of claims 1 to 3.

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