Polymer antibacterial material and preparation method thereof

Abstract

The invention relates to the technical field of polymer materials, and discloses a polymer antibacterial material and a preparation method thereof.The polymer antibacterial material is obtained by adding polyethylene, maleic anhydride grafted polyethylene and quaternary ammonium salt modified polyurethane into a twin-screw extruder, blending and extruding. In the extrusion process, a terminal hydroxyl group in quaternary ammonium salt modified polyurethane reacts with an anhydride group in maleic anhydride grafted polyethylene, so that the compatibility between the quaternary ammonium salt modified polyurethane and polyethylene is increased, and meanwhile, crosslinking is generated, so that the quaternary ammonium salt modified polyurethane and the maleic anhydride grafted polyethylene are connected more tightly, and the mechanical properties of the quaternary ammonium salt modified polyurethane and the maleic anhydride grafted polyethylene are improved. A quaternary ammonium salt group and a quaternary phosphonium salt group in the quaternary ammonium salt modified polyurethane have good antibacterial effects and have synergistic antibacterial effects. A silicon element, a phosphorus element and a triazine group in the quaternary ammonium salt modified polyurethane jointly form an antibacterial system, and a synergistic antibacterial effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a polymer antibacterial material and a preparation method thereof. Background Art

[0002] With the development of industry, more and more bacterial infections pose a huge threat to human health and life, so how to avoid this phenomenon is the key to solving the problem. The application of styrene-based polymer materials in our lives can be seen everywhere, but their antibacterial, tensile and flame retardant effects are poor, which greatly limits their application fields. For example, patent CN110591184B discloses a styrene-based polymer antibacterial material and its preparation method. The antibacterial material of the invention has stable chemical properties, high-efficiency and long-lasting antibacterial performance, is harmless to the human body and friendly to the environment, but its flame retardant and mechanical properties have not been improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a polymer antibacterial material and a preparation method thereof, which has good flame retardant, antibacterial and tensile resistance effects.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a polymer antibacterial material, comprising the following weight components: 60-100 parts by weight of polyethylene, 25-32 parts by weight of maleic anhydride grafted polyethylene, and 5-10 parts by weight of quaternary ammonium salt modified polyurethane.

[0007] Preferably, the preparation method of the quaternary ammonium salt modified polyurethane is:

[0008] (1) 0.65-0.8 g of chitosan is dissolved in an acetic acid solution with a mass fraction of 0.8-1%, and then 0.01-0.02 g of an initiator 1-hydroxybenzotriazole monohydrate is added to react for 0.5-0.6 h, and then 0.2-0.6 g of (3-carboxypropyl) triphenylphosphonium bromide is added thereto, and nitrogen is introduced for protection, and the reaction is carried out at 75-90° C. for 20-25 h, and then 0.6-0.8 g of salicylic acid is added, and the reaction is continued for 0.4-0.6 h. After the reaction is completed, the chitosan is dialyzed for 2-3 days using a dialysis bag with a molecular weight cutoff of 3500 to obtain a modified chitosan;

[0009] (2) Add 12-14 g of octamethylcyclotetrasiloxane and 1-2 g of 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, add 10-12 mg of catalyst in a nitrogen atmosphere, heat to 110-125° C., react for 5-8 h, then heat to 130-140° C., react for 3-5 h, cool and discharge to obtain a double-terminal epoxy silicone oil;

[0010] (3) adding modified chitosan and double-terminal epoxy silicone oil to N,N-dimethylformamide solvent, stirring evenly, adding boron trifluoride ether catalyst, continuing to react at 75-90° C. for 8-10 hours, and then performing reduced pressure distillation and washing to obtain silicon-modified chitosan;

[0011] (4) After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then drop dibutyltin dilaurate as a catalyst, react at 50-80° C. for 2-4 hours to perform prepolymerization, then add silicon-modified chitosan and quaternary ammonium salt chain extender, stir to continue chain extension reaction, react at 50-65° C. for 4-7 hours, and after the reaction is completed, cool and discharge to obtain quaternary ammonium salt modified polyurethane.

[0012] Preferably, the catalyst in (2) is tetramethylammonium hydroxide.

[0013] Preferably, the mass ratio of the modified chitosan, double-ended epoxy silicone oil and boron trifluoride etherate catalyst in (3) is 1:1.2-1.3:0.01-0.02.

[0014] Preferably, the mass ratio of the polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, silicon-modified chitosan, and quaternary ammonium salt chain extender in (4) is 1.2-2:1:0.01-0.02:0.4-0.8:0.5-0.7.

[0015] Preferably, the preparation method of the quaternary ammonium salt chain extender in (4) is:

[0016] S1. Add 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and lysine to isopropanol solvent, stir and mix, heat to 30-50°C, react for 6-10h, then continue to add tris(dimethylamino)silane and chloroplatinic acid catalyst, react at 70-95°C for 8-12h, filter and wash after completion to obtain triazine silane;

[0017] S2. Add 7-12 g of triazine silane and 7-16 g of chloroethanol into N,N-dimethylformamide solvent, stir to dissolve, stir for 10-15 min, heat to 70-90 ° C for quaternization reaction, and after the reaction, distill under reduced pressure, wash and dry to obtain a quaternary ammonium salt chain extender.

[0018] Preferably, the mass ratio of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine, lysine, tris(dimethylamino)silane and chloroplatinic acid catalyst in S1 is 1:2.1-3.2:2.4-3.5:0.01-0.02.

[0019] Preferably, the preparation method of the polymer antibacterial material is: adding polyethylene, maleic anhydride grafted polyethylene, and quaternary ammonium salt modified polyurethane into a twin-screw extruder, with a blending temperature of 180-190° C. and an extrusion temperature of 170-180° C. to obtain the polymer antibacterial material.

[0020] (III) Beneficial technical effects

[0021] The invention obtains the high molecular antibacterial material by adding polyethylene, maleic anhydride grafted polyethylene and quaternary ammonium salt modified polyurethane into a twin-screw extruder, blending and extruding.

[0022] The amino group in chitosan and the carboxyl group in (3-carboxypropyl)triphenylphosphonium bromide are subjected to an amidation reaction, and salicylic acid is added to react to introduce phenolic hydroxyl groups, thereby obtaining modified chitosan; the phenolic hydroxyl groups in the modified chitosan and the epoxy groups of the double-terminal epoxy silicone oil are subjected to an addition reaction to introduce hydroxyl groups, thereby obtaining silicon-modified chitosan; the aldehyde group in 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and the amino group in lysine are subjected to a condensation reaction, and then Then, tri(dimethylamino)silane is added to carry out addition reaction, and a tertiary amine group is introduced to obtain triazine silane; the tertiary amine group in the triazine silane and the chlorine group in the chloroethanol are subjected to quaternization reaction to obtain a quaternary ammonium salt chain extender; the polyether diol is dehydrated and mixed evenly with hexamethylene diisocyanate, and then a dibutyltin dilaurate catalyst is added dropwise to carry out prepolymerization, and then silicon-modified chitosan and the quaternary ammonium salt chain extender are added, and the chain extension reaction is continued with stirring to obtain a quaternary ammonium salt modified polyurethane.

[0023] During the extrusion process, the terminal hydroxyl groups in the quaternary ammonium salt modified polyurethane react with the anhydride groups in the maleic anhydride grafted polyethylene, increasing the compatibility with polyethylene and generating cross-linking, making the connection tighter and increasing its mechanical properties. The quaternary ammonium salt groups and quaternary phosphonium salt groups in the quaternary ammonium salt modified polyurethane have good antibacterial effects and synergistic antibacterial effects. The silicon element, phosphorus element, and triazine group in the quaternary ammonium salt modified polyurethane together constitute an antibacterial system and synergistic antibacterial effects. DETAILED DESCRIPTION

[0024] Example 1

[0025] (1) 0.65 g of chitosan was dissolved in 0.8% acetic acid solution, and then 0.01 g of initiator 1-hydroxybenzotriazole monohydrate was added to react for 0.5 h, and then 0.2 g of (3-carboxypropyl) triphenylphosphonium bromide was added thereto, and nitrogen was introduced for protection, and the reaction was carried out at 75° C. for 20 h, and then 0.6 g of salicylic acid was added, and the reaction was continued for 0.4 h. After the reaction was completed, the reaction was dialyzed for 2 days using a dialysis bag with a molecular weight cutoff of 3500 to obtain modified chitosan;

[0026] (2) Add 12 g of octamethylcyclotetrasiloxane and 1 g of 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, add 10 mg of tetramethylammonium hydroxide catalyst in a nitrogen atmosphere, heat to 110° C., react for 5 h, then heat to 130° C., react for 3 h, cool and discharge to obtain a double-ended epoxy silicone oil;

[0027] (3) Add 1 g of modified chitosan and 1.2 g of double-ended epoxy silicone oil to N,N-dimethylformamide solvent, stir evenly, continue to add 0.01 g of boron trifluoride ether catalyst, continue to react at 75° C. for 8 h, and then perform reduced pressure distillation and washing to obtain silicon-modified chitosan;

[0028] (4) Add 1 g of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and 2.1 g of lysine to an isopropanol solvent, stir and mix, heat to 30° C., react for 6 h, then continue to add 2.4 g of tris(dimethylamino)silane and 0.01 g of chloroplatinic acid catalyst, react at 70° C. for 8 h, filter and wash after completion to obtain triazine silane;

[0029] (5) adding 7 g of triazine silane and 7 g of chloroethanol to N,N-dimethylformamide solvent, stirring to dissolve, stirring for 10 min, heating to 70° C. to carry out quaternization reaction, and after the reaction, distilling under reduced pressure, washing and drying to obtain a quaternary ammonium salt chain extender;

[0030] (6) 1.2 g of polyether diol was dehydrated and mixed with 1 g of hexamethylene diisocyanate, nitrogen was introduced, and then 0.01 g of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 50° C. for 2 h to perform prepolymerization, and then 0.4 g of silicon-modified chitosan and 0.5 g of quaternary ammonium salt chain extender were added, and the chain extension reaction was continued by stirring, and the mixture was reacted at 50° C. for 4 h. After the reaction was completed, the mixture was cooled and discharged to obtain a quaternary ammonium salt modified polyurethane;

[0031] (7) 60 parts by weight of polyethylene, 25 parts by weight of maleic anhydride grafted polyethylene, and 5 parts by weight of quaternary ammonium salt modified polyurethane are added into a twin-screw extruder at a blending temperature of 180° C. and an extrusion temperature of 170° C. to obtain a polymer antibacterial material.

[0032] Example 2

[0033] (1) 0.8 g of chitosan was dissolved in a 1% acetic acid solution, and then 0.02 g of an initiator 1-hydroxybenzotriazole monohydrate was added to react for 0.6 h, and then 0.6 g of (3-carboxypropyl) triphenylphosphonium bromide was added thereto, and nitrogen was introduced for protection, and the reaction was carried out at 90° C. for 25 h, and then 0.8 g of salicylic acid was added, and the reaction was continued for 0.6 h. After the reaction was completed, the reaction was dialyzed for 3 days using a dialysis bag with a molecular weight cutoff of 3500 to obtain modified chitosan;

[0034] (2) Add 14 g of octamethylcyclotetrasiloxane and 2 g of 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, add 12 mg of tetramethylammonium hydroxide catalyst in a nitrogen atmosphere, heat to 125° C., react for 8 h, then heat to 140° C., react for 5 h, cool and discharge to obtain a double-terminal epoxy silicone oil;

[0035] (3) Add 1 g of modified chitosan and 1.3 g of double-ended epoxy silicone oil to N,N-dimethylformamide solvent, stir evenly, continue to add 0.02 g of boron trifluoride ether catalyst, continue to react at 90° C. for 10 h, and then perform reduced pressure distillation and washing to obtain silicon-modified chitosan;

[0036] (4) Add 1 g of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and 3.2 g of lysine to an isopropanol solvent, stir and mix, heat to 50° C., react for 10 h, then continue to add 3.5 g of tris(dimethylamino)silane and 0.02 g of chloroplatinic acid catalyst, react at 95° C. for 12 h, filter and wash after completion to obtain triazine silane;

[0037] (5) adding 12 g of triazine silane and 16 g of chloroethanol to N,N-dimethylformamide solvent, stirring to dissolve, stirring for 15 min, heating to 90 ° C. to carry out quaternization reaction, and after the reaction, distilling under reduced pressure, washing and drying to obtain a quaternary ammonium salt chain extender;

[0038] (6) 2 g of polyether diol was dehydrated and mixed with 1 g of hexamethylene diisocyanate, nitrogen was introduced, and then 0.02 g of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 80° C. for 4 h for prepolymerization, and then 0.8 g of silicon-modified chitosan and 0.7 g of quaternary ammonium salt chain extender were added, and the chain extension reaction was continued by stirring, and the mixture was reacted at 65° C. for 7 h. After the reaction was completed, the mixture was cooled and discharged to obtain a quaternary ammonium salt modified polyurethane;

[0039] (7) 100 parts by weight of polyethylene, 32 parts by weight of maleic anhydride grafted polyethylene, and 10 parts by weight of quaternary ammonium salt modified polyurethane are added into a twin-screw extruder at a blending temperature of 190° C. and an extrusion temperature of 180° C. to obtain a polymer antibacterial material.

[0040] Example 3

[0041] (1) 0.7 g of chitosan was dissolved in a 0.9% acetic acid solution, and then 0.01 g of an initiator 1-hydroxybenzotriazole monohydrate was added to react for 0.55 h, and then 0.5 g of (3-carboxypropyl) triphenylphosphonium bromide was added thereto, and nitrogen was introduced for protection, and the reaction was carried out at 85° C. for 22 h, and then 0.7 g of salicylic acid was added, and the reaction was continued for 0.5 h. After the reaction was completed, the reaction was dialyzed for 2 days using a dialysis bag with a molecular weight cutoff of 3500 to obtain modified chitosan;

[0042] (2) Add 13 g of octamethylcyclotetrasiloxane and 1 g of 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, add 11 mg of tetramethylammonium hydroxide catalyst in a nitrogen atmosphere, heat to 120° C., react for 7 h, then heat to 135° C., react for 4 h, cool and discharge to obtain a double-ended epoxy silicone oil;

[0043] (3) Add 1 g of modified chitosan and 1.2 g of double-ended epoxy silicone oil to N,N-dimethylformamide solvent, stir evenly, continue to add 0.015 g of boron trifluoride ether catalyst, continue to react at 85° C. for 9 h, and then perform reduced pressure distillation and washing to obtain silicon-modified chitosan;

[0044] (4) Add 1 g of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and 2.6 g of lysine to an isopropanol solvent, stir and mix, heat to 35° C., react for 8 h, then continue to add 2.8 g of tris(dimethylamino)silane and 0.01 g of chloroplatinic acid catalyst, react at 80° C. for 10 h, filter and wash after completion to obtain triazine silane;

[0045] (5) adding 9 g of triazine silane and 12 g of chloroethanol to N,N-dimethylformamide solvent, stirring to dissolve, stirring for 12 min, heating to 80 ° C. to carry out quaternization reaction, and after the reaction, distilling under reduced pressure, washing and drying to obtain a quaternary ammonium salt chain extender;

[0046] (6) 1.6 g of polyether diol was dehydrated and mixed with 1 g of hexamethylene diisocyanate, nitrogen was introduced, and then 0.01 g of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 75° C. for 3 h to perform prepolymerization, and then 0.6 g of silicon-modified chitosan and 0.5 g of quaternary ammonium salt chain extender were added, and the chain extension reaction was continued by stirring, and the mixture was reacted at 50° C. for 7 h. After the reaction was completed, the mixture was cooled and discharged to obtain a quaternary ammonium salt modified polyurethane;

[0047] (7) 80 parts by weight of polyethylene, 30 parts by weight of maleic anhydride grafted polyethylene, and 8 parts by weight of quaternary ammonium salt modified polyurethane are added into a twin-screw extruder at a blending temperature of 185° C. and an extrusion temperature of 175° C. to obtain a polymer antibacterial material.

[0048] Example 4

[0049] (1) 0.65 g of chitosan was dissolved in 0.8% acetic acid solution, and then 0.01 g of initiator 1-hydroxybenzotriazole monohydrate was added to react for 0.5 h, and then 0.2 g of (3-carboxypropyl) triphenylphosphonium bromide was added thereto, and nitrogen was introduced for protection, and the reaction was carried out at 75° C. for 20 h, and then 0.6 g of salicylic acid was added, and the reaction was continued for 0.4 h. After the reaction was completed, the reaction was dialyzed for 2 days using a dialysis bag with a molecular weight cutoff of 3500 to obtain modified chitosan;

[0050] (2) Add 12 g of octamethylcyclotetrasiloxane and 1 g of 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, add 10 mg of tetramethylammonium hydroxide catalyst in a nitrogen atmosphere, heat to 110° C., react for 5 h, then heat to 130° C., react for 3 h, cool and discharge to obtain a double-ended epoxy silicone oil;

[0051] (3) Add 1 g of modified chitosan and 1.3 g of double-ended epoxy silicone oil to N,N-dimethylformamide solvent, stir evenly, continue to add 0.02 g of boron trifluoride ether catalyst, continue to react at 90° C. for 10 h, and then perform reduced pressure distillation and washing to obtain silicon-modified chitosan;

[0052] (4) Add 1 g of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and 3.2 g of lysine to an isopropanol solvent, stir and mix, heat to 50° C., react for 10 h, then continue to add 3.5 g of tris(dimethylamino)silane and 0.02 g of chloroplatinic acid catalyst, react at 95° C. for 12 h, filter and wash after completion to obtain triazine silane;

[0053] (5) adding 9 g of triazine silane and 12 g of chloroethanol to N,N-dimethylformamide solvent, stirring to dissolve, stirring for 12 min, heating to 80 ° C. to carry out quaternization reaction, and after the reaction, distilling under reduced pressure, washing and drying to obtain a quaternary ammonium salt chain extender;

[0054] (6) 1.6 g of polyether diol was dehydrated and mixed with 1 g of hexamethylene diisocyanate, nitrogen was introduced, and then 0.01 g of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 75° C. for 3 h to perform prepolymerization, and then 0.6 g of silicon-modified chitosan and 0.5 g of quaternary ammonium salt chain extender were added, and the chain extension reaction was continued by stirring, and the mixture was reacted at 50° C. for 7 h. After the reaction was completed, the mixture was cooled and discharged to obtain a quaternary ammonium salt modified polyurethane;

[0055] (7) 80 parts by weight of polyethylene, 30 parts by weight of maleic anhydride grafted polyethylene, and 8 parts by weight of quaternary ammonium salt modified polyurethane are added into a twin-screw extruder at a blending temperature of 185° C. and an extrusion temperature of 175° C. to obtain a polymer antibacterial material.

[0056] Comparative Example 1

[0057] 80 parts by weight of polyethylene and 30 parts by weight of maleic anhydride grafted polyethylene were added into a twin-screw extruder at a blending temperature of 185° C. and an extrusion temperature of 175° C. to obtain a polymer antibacterial material.

[0058] A Staphylococcus aureus liquid with a concentration of 2×108 CFU / mL was added as a test strain to a sterilized culture dish, and then a solid agar medium was added and dissolved, cooled to 45°C, and then poured into a culture dish, 20 mL was poured into each plate with an inner diameter of 10 cm, and then the antibacterial materials of the embodiments of the present invention and the comparative example (with a diameter of 3 cm and a thickness of 1 mm) were placed on the culture plate, and cultured in a constant temperature incubator for 12 hours at a temperature of 37°C. After culture, the diameter of the inhibition zone was measured. The test results are shown in Table 1.

[0059] Table 1: Antimicrobial testing.

[0060]

[0061]

[0062] It can be seen from Table 1 that the diameter of the antibacterial zone of the polymer antibacterial material of the present invention reaches 16.3-17.4 mm, indicating that it has a good antibacterial effect.

[0063] The tensile properties of the material were tested using an electronic universal testing machine. The test results are shown in Table 2.

[0064] Table 2: Tensile properties tested.

[0065] project Tensile properties (MPa) Example 1 41.9 Example 2 43.6 Example 3 42.5 Example 4 42.7 Comparative Example 1 22.8

[0066] As can be seen from Table 2, the tensile properties of the polymer antibacterial material of the present invention reach 42.5-43.6 MP, indicating that it has good tensile properties and therefore good mechanical properties.

[0067] The oxygen index of the polymer antibacterial material is tested with an oxygen index tester, and the combustion level of the polymer antibacterial material is tested with a horizontal and vertical combustion tester.

[0068] Table 3: Flame retardancy test.

[0069] project Oxygen index (%) UL-94 Example 1 28 V-0 Example 2 29 V-0 Example 3 28 V-0 Example 4 27 V-0 Comparative Example 1 21 V-1

[0070] It can be seen from Table 3 that Examples 1-4 of the present invention have better flame retardant effects than Comparative Example 1.

[0071] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A polymer antibacterial material, characterized in that: The invention comprises the following components by weight: 60-100 parts by weight of polyethylene, 25-32 parts by weight of maleic anhydride grafted polyethylene, and 5-10 parts by weight of quaternary ammonium salt modified polyurethane.

2. The polymer antibacterial material according to claim 1, characterized in that: The preparation method of the quaternary ammonium salt modified polyurethane is: (1) 0.65-0.8 g of chitosan is dissolved in an acetic acid solution with a mass fraction of 0.8-1%, and then 0.01-0.02 g of an initiator 1-hydroxybenzotriazole monohydrate is added to react for 0.5-0.6 h, and then 0.2-0.6 g of (3-carboxypropyl) triphenylphosphonium bromide is added thereto, and nitrogen is introduced for protection, and the reaction is carried out at 75-90° C. for 20-25 h, and then 0.6-0.8 g of salicylic acid is added, and the reaction is continued for 0.4-0.6 h. After the reaction is completed, the chitosan is dialyzed for 2-3 days using a dialysis bag with a molecular weight cutoff of 3500 to obtain a modified chitosan; (2) Add 12-14 g of octamethylcyclotetrasiloxane and 1-2 g of 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, add 10-12 mg of catalyst in a nitrogen atmosphere, heat to 110-125° C., react for 5-8 h, then heat to 130-140° C., react for 3-5 h, cool and discharge to obtain a double-terminal epoxy silicone oil; (3) adding modified chitosan and double-terminal epoxy silicone oil to N,N-dimethylformamide solvent, stirring evenly, adding boron trifluoride ether catalyst, continuing to react at 75-90° C. for 8-10 hours, and then performing reduced pressure distillation and washing to obtain silicon-modified chitosan; (4) After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then drop dibutyltin dilaurate as a catalyst, react at 50-80° C. for 2-4 hours to perform prepolymerization, then add silicon-modified chitosan and quaternary ammonium salt chain extender, stir to continue chain extension reaction, react at 50-65° C. for 4-7 hours, and after the reaction is completed, cool and discharge to obtain quaternary ammonium salt modified polyurethane.

3. The polymer antibacterial material according to claim 2, characterized in that: The catalyst in (2) is tetramethylammonium hydroxide.

4. The polymer antibacterial material according to claim 2, characterized in that: The mass ratio of the modified chitosan, double-ended epoxy silicone oil and boron trifluoride etherate catalyst in (3) is 1:1.2-1.3:0.01-0.

02.

5. The polymer antibacterial material according to claim 2, characterized in that: The mass ratio of the polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, silicon-modified chitosan and quaternary ammonium salt chain extender in (4) is 1.2-2:1:0.01-0.02:0.4-0.8:0.5-0.

7.

6. The polymer antibacterial material according to claim 2, characterized in that: The preparation method of the quaternary ammonium salt chain extender in (4) is: S1. Add 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and lysine to isopropanol solvent, stir and mix, heat to 30-50°C, react for 6-10h, then continue to add tris(dimethylamino)silane and chloroplatinic acid catalyst, react at 70-95°C for 8-12h, filter and wash after completion to obtain triazine silane; S2. Add 7-12 g of triazine silane and 7-16 g of chloroethanol into N,N-dimethylformamide solvent, stir to dissolve, stir for 10-15 min, heat to 70-90 ° C for quaternization reaction, and after the reaction, distill under reduced pressure, wash and dry to obtain a quaternary ammonium salt chain extender.

7. The polymer antibacterial material according to claim 6, characterized in that: The mass ratio of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine, lysine, tris(dimethylamino)silane and chloroplatinic acid catalyst in S1 is 1:2.1-3.2:2.4-3.5:0.01-0.

02.

8. A method for preparing a polymer antibacterial material according to any one of claims 1 to 7, characterized in that: The preparation method of the polymer antibacterial material is as follows: polyethylene, maleic anhydride grafted polyethylene and quaternary ammonium salt modified polyurethane are added into a twin-screw extruder, the blending temperature is 180-190° C., the extrusion temperature is 170-180° C., and the polymer antibacterial material is obtained.

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