A fluorine-containing pyridinium salt polychloramine bactericidal polymer and its preparation method and application

Abstract

The present invention relates to a bactericidal polymer, in particular to a fluorine-containing pyridinium salt polychloramine bactericidal polymer, and a preparation method and application thereof. The polymer is a combination of a pyridinium salt and a tetrahalamine salt, and is compounded by combining two types of readily available bactericidal groups to improve bactericidal performance and bactericidal stability through their synergistic effect. Fluorine-containing halogenated alkanes with heteroatom sulfur are introduced into the polymer, and the characteristics of the halogenated alkanes can be utilized to concentrate the bactericidal polymer on the surface of the bactericidal layer and allow the bactericidal polymer to contact pathogens as much as possible, thereby achieving the purpose of rapid and efficient bactericidal treatment.

Description

Technical Field

[0001] The present invention relates to a bactericidal polymer, in particular to a fluorine-containing pyridinium salt polychloramine bactericidal polymer and a preparation method and application thereof. Background Art

[0002] Fungicides are widely used in daily life. Highly efficient fungicides can not only provide a safe living environment for humans, but also serve as auxiliary materials to improve the use value of other functional materials and provide guarantees for the efficacy of functional materials.

[0003] There are many types of known pathogens, and their properties and structures vary greatly. During use, small molecule fungicides cannot achieve efficient and rapid sterilization in complex environments due to the relatively single bactericidal groups they contain. Prolonging the sterilization time can easily cause pathogens to develop drug resistance, thereby reducing their bactericidal performance.

[0004] Therefore, small molecule fungicides with a single bactericidal group can no longer provide a good killing effect. The preparation of composite bactericidal polymers has become the main development trend at present: combining multiple bactericidal groups and using their synergistic effect to expand the bactericidal range and improve the bactericidal efficiency. At the same time, composite high-efficiency fungicides can also make up for the problem of few action points, weak binding force and easy falling off between small molecule fungicides and substrates. It can not only prolong the bactericidal effect, but also prevent the separation of fungicides and substrates from endangering human health, providing a safer sterilization environment.

[0005] Quaternary ammonium salt fungicides are one of the most common fungicides on the market. They contain positively charged nitrogen atoms, which can attract negatively charged bacteria. Upon contact, they can penetrate the cell wall and destroy the cell membrane structure, leading to the death of the bacteria. During the research process, the experimenters found that halamine fungicides also use positively charged halogens for oxidation and sterilization, and polymers containing both quaternary ammonium salt and halamine bactericidal groups can have a bactericidal efficiency that exceeds the bactericidal efficiency of any single group, showing a good synergistic effect.

[0006] Furthermore, during the experiment, the researchers discovered that the presence of fluorinated compounds can improve sterilization efficiency. Therefore, they considered using fluorinated halogenated alkanes as alkylating agents to introduce into the composite bactericidal polymer. Taking advantage of the low surface tension of fluorinated compounds, the bactericide could be migrated to the outermost surface of the bactericidal layer, facilitating contact and killing of pathogens. However, when fluorinated compounds are introduced into a polar environment, the carbon fluorocarbons flip to the sublayer while the polar components flip to the outermost layer, ultimately losing their low-tension surface. While this facilitates the insertion of the rigid carbon fluorocarbon segments into the bacteria for sterilization, the high hydrophobicity may hinder the wetting of the bactericide surface and the contact area with the bacteria.

[0007] In summary, there is an urgent need for a composite bactericidal polymer that can deal with multiple pathogens or pathogen combinations. Such a composite bactericidal polymer not only needs to combine and compound multiple functional groups with bactericidal properties to maximize their synergistic effect, improve the applicability and bactericidal efficiency of the bactericide, and avoid the development of drug resistance in pathogens due to long-term use, but also needs to reconstruct the structure of the introduced functional groups to reduce the possibility that the introduced functional groups may cause or lead to negative effects in the bactericidal process. Summary of the Invention

[0008] The purpose of the present invention is to provide a fluorine-containing pyridinium salt polychloramine bactericidal polymer;

[0009] Another object of the present invention is to provide a preparation method and application of a fluorine-containing pyridinium salt polychloramine bactericidal polymer.

[0010] The technical solution adopted to achieve the purpose of the present invention is:

[0011] To solve the problems mentioned in the background technology, the present application is a fluorine-containing pyridinium salt polychloramine bactericidal polymer, which uses a silane polymer as a base and introduces two types of bactericidal groups, a pyridinium salt and four halamines, into the structure.

[0012] The silane polymer structure is Where p is any integer between 1 and 11.

[0013] Single-chain pyridinium salts are selected in fluorinated pyridinium salt polychloramine bactericidal polymers because single-chain pyridinium salts are less affected by steric hindrance during the polymer synthesis process and encounter less resistance when penetrating the cell wall than double-chain pyridinium salts or polypyridinium salts, thereby improving the efficiency of destroying bacteria; single-chain pyridinium salts only occupy one nitrogen binding site, so they can bind more halogens to increase the number of halamine bactericidal groups. Since halamine bactericides have higher bactericidal efficiency than pyridinium salt bactericides, have a wide bactericidal range, are renewable, and are not prone to drug resistance, the structure of monopyridinium salts and tetrahalamines can achieve better bactericidal efficiency and increase the types and number of bactericidal groups.

[0014] At the same time, fluorinated halogenated alkanes are used as alkylating agents, and their low surface tension is utilized to reduce the surface tension of the bactericidal polymer, thereby enriching the bactericidal groups on the surface. This allows the bactericidal groups to be oriented at a shallower depth for better contact with bacteria, fully leveraging the synergistic effect brought by the multifunctional groups of pyridinium salts and tetrahalamines and the efficient bactericidal ability of halamines, thereby improving the bactericidal performance; and the fluorinated halogenated alkanes are reconstructed by introducing sulfur atoms between the CH and CF groups to improve their directional ability, flexibility, rigidity, steric hindrance, surface hydrophilicity and other properties, thereby obtaining different structure-activity relationships.

[0015] The fluorine-containing pyridinium salt polychloramine bactericidal polymer has the structure of the following formula (1):

[0016]

[0017]

[0018] Wherein, X is a halogen;

[0019] n is any integer between 2 and 4;

[0020] m is any integer between 2 and 4;

[0021] p is any integer between 1 and 11;

[0022] Further, X is halogen;

[0023] n is 2 or 4;

[0024] m is 4;

[0025] p is any integer between 1 and 11;

[0026] Furthermore, X is Cl or Br;

[0027] n is any integer between 2 and 4;

[0028] m is any integer between 2 and 4;

[0029] p is any integer between 1 and 11;

[0030] Furthermore, X is any one of Cl or Br;

[0031] n is 2 or 4;

[0032] m is 4;

[0033] p is any integer between 1 and 11.

[0034] The present application also relates to a method for preparing a fluorine-containing pyridinium salt polychloramine bactericidal polymer, the reaction formula of which is as follows: S1: Preparation of fluorine-containing bromoalkane, the reaction formula of which is as follows

[0035]

[0036] n is any integer between 2 and 4;

[0037] m is any integer between 2 and 4;

[0038] Azobisisobutyronitrile is added to 1-iodoperfluoropentane and 5-hexen-1-ol during the reaction process, and after the reaction, anhydrous ether and sodium dihydrobis(dimethoxyethoxy)aluminate are added respectively, p-toluenesulfonyl chloride and sodium hydroxide are added to the obtained product, and then 4-bromobutanethiol is added and the mixture is heated under reflux to obtain a fluorine-containing bromoalkane;

[0039] Furthermore, azobisisobutyronitrile was added to 1-iodoperfluoropentane and 5-hexen-1-ol in four portions at 80° C., and the mixture was reacted for 8 hours before vacuum distillation. Anhydrous ether and sodium dihydrobis(dimethoxyethoxy)aluminate were then added, respectively, and the mixture was reacted at room temperature for 3 hours, followed by purification. p-Toluenesulfonyl chloride and sodium hydroxide were added to the obtained product, and the mixture was heated under reflux for 4 hours before purification. 4-Bromobutanethiol was added to the purified product, and the mixture was heated under reflux for 6 hours, and the fluorine-containing bromoalkane was obtained after purification.

[0040] Further, 0.025 mole fraction of azobisisobutyronitrile was added four times to 5 mole fraction of 1-iodoperfluoropentane and 7.5 mole fraction of 5-hexen-1-ol at 80° C., and the mixture was reacted for 8 hours before vacuum distillation. 15 mole fraction of anhydrous ether and 6.5 mole fraction of sodium dihydrobis(dimethoxyethoxy)aluminate were added respectively, and the mixture was reacted at room temperature for 3 hours before purification. The purification process included extraction with dichloromethane, drying with anhydrous MgSO4, and vacuum distillation. 7.5 mole fraction of p-toluenesulfonyl chloride and 0.5 mole fraction of sodium hydroxide were added to the obtained product, and the mixture was heated under reflux for 4 hours for purification. 7.5 mole fraction of 4-bromobutanethiol was added to the purified product, and the mixture was heated under reflux for 6 hours before purification. The purification process included first adding 50 mole fraction of ether to dissolve the mixture, and then purifying the mixture through a short silica gel column using ether as an eluent to obtain a fluorine-containing bromoalkane.

[0041] S2: Preparation of bactericidal precursor, the reaction formula is as follows:

[0042]

[0043] Through a nucleophilic substitution reaction, 2-aminobarbituric acid and allylsuccinic anhydride are added to the solution, dissolved, and then refluxed to bond 2-aminobarbituric acid and allylsuccinic anhydride to prepare a bactericidal precursor;

[0044] Further, the solution is anhydrous DMSO;

[0045] Furthermore, 2-aminobarbituric acid and allylsuccinic anhydride were dissolved in anhydrous DMSO, refluxed for 4 hours, and distilled after the reaction to obtain a bactericidal precursor;

[0046] Further, 5 mol fractions of 2-aminobarbituric acid and 5 mol fractions of allylsuccinic anhydride were dissolved in 20 mol fractions of anhydrous DMSO, refluxed for 4 hours, and distilled after the reaction to obtain a bactericidal precursor;

[0047] S3: The bactericidal precursor is bonded to 4-aminopyridine, and the reaction formula is as follows:

[0048]

[0049] dissolving the bactericidal precursor and 4-aminopyridine in a solution to complete the bonding of the bactericidal precursor and 4-aminopyridine;

[0050] Furthermore, the solution is a mixed solution of EDC and sNHS;

[0051] Furthermore, the bactericidal precursor and 4-aminopyridine were dissolved in a mixed solution of EDC and sNHS, and reacted at room temperature for 10 hours to complete the bonding between the bactericidal precursor and 4-aminopyridine;

[0052] Furthermore, 5 mol fractions of the bactericidal precursor and 5 mol fractions of 4-aminopyridine were dissolved in a mixed solution of 15 mol fractions of EDC and 30 mol fractions of sNHS, and reacted at room temperature for 10 hours to complete the bonding of the bactericidal precursor and 4-aminopyridine;

[0053] S4: Preparation of pyridinium salt product, the reaction formula is as follows:

[0054]

[0055] Where: n is any integer between 2 and 4;

[0056] m is any integer between 2 and 4;

[0057] The fluorine-containing bromoalkane prepared by S1 is added to the S3 product and refluxed, and the fluorine-containing bromoalkane prepared by S1 is used to convert the tertiary amine in the S3 product into a pyridinium salt to obtain a pyridinium salt product;

[0058] Further, the fluorine-containing bromoalkane prepared in S1 was added to the S3 product and refluxed for 10 hours, and the pyridinium salt product was obtained after purification;

[0059] Further, 8 mole fractions of the fluorine-containing bromoalkane prepared by S1 were added to the S3 product, refluxed for 10 hours, and the product was purified by using tetrahydrofuran as the eluent and purified on a silica gel column to obtain a pyridine salt product;

[0060] S5: The pyridinium salt product is bonded to the hydrogenated silicone oil through a hydrosilation reaction. The reaction formula is as follows:

[0061]

[0062] Where: n is any integer between 2 and 4;

[0063] m is any integer between 2 and 4;

[0064] p is any integer between 1 and 11;

[0065] The pyridinium salt product was dissolved in the solution, the catalyst and P(MHS–DMS) were added, and the reaction was refluxed to obtain the S5 product;

[0066] Where P(MHS–DMS) stands for

[0067] Furthermore, the solution is anhydrous tetrahydrofuran, and the catalyst is a chloroplatinic acid catalyst;

[0068] Furthermore, the pyridinium salt product was dissolved in anhydrous tetrahydrofuran, chloroplatinic acid catalyst and P(MHS–DMS) were added, and the reaction was refluxed for 3 h to obtain product S5;

[0069] Furthermore, 5 mol fraction of the pyridinium salt product was dissolved in 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS–DMS) were added, and the reaction was refluxed for 3 hours to obtain product S5;

[0070] S6: Preparation of fluorine-containing pyridinium salt polychloramine bactericidal polymer, the reaction formula is as follows:

[0071]

[0072] wherein X is a halogen;

[0073] n is any integer between 2 and 4;

[0074] m is any integer between 2 and 4;

[0075] p is any integer between 1 and 11.

[0076] adding a halogenating agent dissolved in a dimethyl sulfoxide solution to the S5 product, treating the S5 product with the halogenating agent to generate a halamine bactericidal group, and obtaining a fluorine-containing pyridinium salt polychloramine bactericidal polymer;

[0077] Further, a halogenating agent dissolved in a dimethyl sulfoxide solution is added to the S5 product, and the mixture is reacted at room temperature for 5 hours, and the fluorine-containing pyridinium salt polychloramine bactericidal polymer is purified;

[0078] Further, a halogenating agent dissolved in an excess of dimethyl sulfoxide solution is added to the S5 product to react to obtain a fluorine-containing pyridinium salt polychloramine bactericidal polymer, and the reaction is carried out at room temperature for 5 hours and then purified. The purification process is to purify the product using tetrahydrofuran as an eluent and a silica gel column to obtain a fluorine-containing pyridinium salt polychloramine bactericidal polymer after purification;

[0079] Furthermore, the halogenating agent is sodium dichloroisocyanurate or sodium dibromoisocyanurate.

[0080] The present application also discloses the use of a fluorine-containing pyridinium salt polychloramine bactericidal polymer having a structure of formula (1) or prepared using the method for preparing a fluorine-containing pyridinium salt polychloramine bactericidal polymer in the preparation of bactericidal cotton sheets and filter columns.

[0081] Compared with the prior art, the present invention has the following beneficial effects:

[0082] 1. The bactericidal polymer of the present application uses silane as a base. When used, the silane is hydrolyzed and can shrink and polymerize on the surface of the material to form a silicone polymer bactericidal layer. The silicone main chain is used to carry a polychloramine bactericidal polymer containing fluorine-containing pyridinium salts for sterilization. The polymer not only contains pyridinium salts and halamines, but also optimizes their ratio in order to maximize the synergistic bactericidal performance between the two groups. It not only has a wide range of applications and high bactericidal efficiency, but also can be used for a long time and has good stability.

[0083] 2. By using fluorinated halogenated alkanes as alkylating agents, the polymer can utilize the characteristics of fluorinated halogenated alkanes to enrich the bactericide on the surface of the formed bactericidal layer. At the same time, heteroatom sulfur is introduced between the CH and CF groups of the fluorinated halogenated alkanes to reconstruct the fluorinated halogenated alkanes, improve their directional ability, flexibility, rigidity, steric hindrance, surface hydrophilicity and other properties, and ensure that the bactericidal polymer can fully contact and kill pathogens. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 This is the infrared spectrum of the polymer of Example 1 of the present invention;

[0085] Figure 2 This is the infrared spectrum of the polymer of Example 3 of the present invention;

[0086] Figure 3 This is the infrared spectrum of the polymer of Example 5 of the present invention. DETAILED DESCRIPTION

[0087] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0088] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0089] Part I Preparation of Polymers

[0090] Example 1 Preparation of Polymer 1

[0091] S1: 5 mol fraction of 1-iodoperfluoropentane and 7.5 mol fraction of 5-hexen-1-ol were added to a 100 mL three-necked flask. 0.025 mol fraction of azobisisobutyronitrile was added in four portions at 80°C for a total of 8 hours. After the reaction, unreacted 5-hexen-1-ol was removed by vacuum distillation. 15 mol fraction of anhydrous ether and 6.5 mol fraction of sodium dihydrogen bis(dimethoxyethoxy)aluminate were then added, and the reaction was continued at room temperature for 3 hours. After the reaction, the product was extracted with dichloromethane, dried over anhydrous MgSO4, and the dichloromethane was removed by vacuum distillation.

[0092] 7.5 mol fractions of p-toluenesulfonyl chloride and 0.5 mol fractions of sodium hydroxide were added to the resulting 6-perfluoropentyl-1-hexanol, and the mixture was heated under reflux for 4 hours. 7.5 mol fractions of 2-bromoethanethiol were added to the purified product, and the mixture was heated under reflux for 6 hours. 50 mol fractions of diethyl ether were added to dissolve the product, and the product was purified by passing it through a short silica gel column using diethyl ether as the eluent to obtain the fluorinated bromoalkane 1.

[0093] The reaction formula is as follows:

[0094]

[0095] S2: 5 mol fraction of 2-aminobarbituric acid, 5 mol fraction of allylsuccinic anhydride, and 20 mol fraction of anhydrous DMSO were added to a 100 mL three-necked flask equipped with a magnetic stirrer and a condenser. Refluxed for 4 hours. After the reaction, the anhydrous DMSO was distilled off to obtain a fungicide precursor containing one amide and two imide-type NH groups.

[0096] The reaction formula is as follows:

[0097]

[0098] S3: Add 5 mole fraction of bactericidal precursor 1, 5 mole fraction of 4-aminopyridine, 15 mole fraction of EDC, and 30 mole fraction of sNHS to a 250 mL three-necked flask and react at room temperature for 10 hours to complete the nucleophilic reaction between bactericidal precursor 1 and 4-aminopyridine. The reaction formula is as follows:

[0099]

[0100] S4: Add 8 mole fractions of fluorine-containing bromoalkane 1 to the above reaction product and reflux for 10 hours to complete the pyridinium salt reaction of the tertiary amine. The product is purified on a silica gel column using tetrahydrofuran as an eluent to obtain the pyridinium salt product 1. The reaction formula is as follows:

[0101]

[0102] S5: 5 mol fraction of pyridinium salt product 1, 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS–DMS) were added to a 250 mL three-necked flask and refluxed for 3 hours to complete the hydrosilylation reaction of the pyridinium salt product and P(MHS–DMS).

[0103] The reaction formula is as follows:

[0104]

[0105] Where: p is any integer between 1 and 11;

[0106] S6: adding an excess of sodium dichloroisocyanurate dissolved in dimethyl sulfoxide solution to the product of S5, and reacting at room temperature for 5 hours to complete the chlorination reaction; the chlorinated product is purified by silica gel column using tetrahydrofuran as eluent to generate a fluorine-containing pyridinium salt polychloramine bactericidal polymer, namely polymer 1.

[0107] The reaction formula is as follows:

[0108]

[0109] Where: p is any integer between 1 and 11;

[0110] The infrared spectrum of polymer 1 is shown in the attached figure. Figure 1 shown.

[0111] Example 2 Preparation of Polymer 2

[0112] S1: 5 mol fractions of 1-iodoperfluoropentane and 7.5 mol fractions of sodium dihydrogen bis(dimethoxyethoxy)aluminate were added to a 100 mL three-necked flask. 0.025 mol fractions of azobisisobutyronitrile were added in four portions at 80°C for a total of 8 hours. After the reaction, unreacted 5-hexen-1-ol was removed by vacuum distillation. 15 mol fractions of anhydrous ether and 6.5 mol fractions of sodium dihydrogen bis(dimethoxyethoxy)aluminate were then added, and the reaction was continued at room temperature for 3 hours. After the reaction, the product was extracted with dichloromethane, dried over anhydrous MgSO4, and the dichloromethane was removed by vacuum distillation.

[0113] 7.5 mol fractions of p-toluenesulfonyl chloride and 0.5 mol fractions of sodium hydroxide were added to the resulting 6-perfluoropentyl-1-hexanol, and the mixture was heated under reflux for 4 hours. 7.5 mol fractions of 4-bromobutanethiol were added to the purified product, and the mixture was heated under reflux for 6 hours. 50 mol fractions of diethyl ether were added to dissolve the product, and the product was purified by passing it through a short silica gel column using diethyl ether as the eluent to obtain the fluorinated bromoalkane 2.

[0114] The reaction formula is as follows:

[0115]

[0116] The reaction process of S2 and S3 is the same as that of S2 and S3 in Example 1;

[0117] S4: Add 8 mol fractions of fluorine-containing bromoalkane 2 to the product of S3 and reflux for 10 hours to complete the pyridinium salt reaction of the tertiary amine; the product is purified on a silica gel column using tetrahydrofuran as an eluent to obtain the pyridinium salt product 2.

[0118] The reaction formula is as follows:

[0119]

[0120] S5: 5 mol fraction of pyridinium salt product 2, 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS–DMS) were added to a 250 mL three-necked flask and refluxed for 3 hours to complete the hydrosilylation reaction of the pyridinium salt product and triethoxysilane.

[0121] The reaction formula is as follows:

[0122]

[0123] Where: p is any integer between 1 and 11;

[0124] S6: An excess amount of sodium dichloroisocyanurate in dimethyl sulfoxide is added to the product of S5 and the reaction is carried out at room temperature for 5 hours to complete the chlorination reaction. The chlorinated product is purified on a silica gel column using tetrahydrofuran as an eluent to produce a fluorinated pyridinium salt polychloramine bactericidal polymer, namely, polymer 2.

[0125] The reaction formula is as follows:

[0126]

[0127] Wherein: p is any integer between 1 and 11.

[0128] Example 3 Preparation of Polymer 3

[0129] In the preparation steps of polymer 3, the preparation process of S1-S5 is the same as the preparation process of S1-S5 in Example 1.

[0130] S6: Add an excess of sodium dibromoisocyanurate dissolved in dimethyl sulfoxide solution to the product of S5 and react at room temperature for 5 hours to complete the bromination reaction. The brominated product is purified on a silica gel column using tetrahydrofuran as the eluent to produce a fluorinated pyridinium salt polybrominamine fungicidal polymer. The reaction formula is as follows:

[0131]

[0132] Where: p is any integer between 1 and 11;

[0133] The infrared spectrum of polymer 3 is shown in the attached figure. Figure 2 shown.

[0134] Example 4 Preparation of Polymer 4

[0135] S1: 5 mol fraction of 1-iodoperfluoropentane and 7.5 mol fraction of 5-hexen-1-ol were added to a 100 mL three-necked flask. 0.025 mol fraction of azobisisobutyronitrile was added in four portions at 80°C over 8 hours. Unreacted 5-hexen-1-ol was removed by vacuum distillation. 15 mol fraction of anhydrous ether and 6.5 mol fraction of sodium dihydrobis(dimethoxyethoxy)aluminate were added, and the mixture was allowed to react at room temperature for 3 hours. After the reaction, the mixture was extracted with dichloromethane, dried over anhydrous MgSO₄, and the dichloromethane was removed by vacuum distillation. 5 mol fraction of 6-perfluoropentyl-1-hexanol and 7.5 mol fraction of triphenylphosphine were dissolved in dry dichloromethane and stirred continuously at -5°C for 1 hour, then at room temperature for another 6 hours. Approximately 80 mL of ether was added for dissolution, and the mixture was then purified by passing through a short silica gel column using ether as the eluent to obtain fluorinated bromoalkane 4.

[0136]

[0137] The reaction process of S2-S3 is the same as the reaction process of S2-S3 in Example 1.

[0138] S4: Add 8 mol fractions of fluorine-containing bromoalkane 4 to the product of S3 and reflux for 10 hours to complete the pyridinium salt reaction of the tertiary amine; the product is purified on a silica gel column using tetrahydrofuran as an eluent to obtain the pyridinium salt product 4.

[0139]

[0140] S5: 5 mol fraction of pyridinium salt product 4, 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS–DMS) were added to a 250 mL three-necked flask and refluxed for 3 hours to complete the hydrosilylation reaction of the pyridinium salt product with triethoxysilane.

[0141] The reaction formula is as follows:

[0142]

[0143] Where p is any integer between 1 and 11;

[0144] S6: Add an excess of sodium dichloroisocyanurate dissolved in dimethyl sulfoxide solution to the product of S5 and react at room temperature for 5 hours to complete the bromination reaction; the brominated product is purified on a silica gel column using tetrahydrofuran as an eluent to produce polymer 4.

[0145] The reaction formula is as follows:

[0146]

[0147] Where p is any integer between 1 and 11.

[0148] Example 5 Preparation of Polymer 5

[0149] During the preparation of polymer 5, the preparation method of S2 and S3 in Example 1 was first used to prepare the product of step S3, and then the subsequent reactions were carried out.

[0150] 8 mol fractions of 1-bromotridecane were added to the above-mentioned S3 product, and the mixture was refluxed for 10 hours to complete the pyridinium salt reaction of the tertiary amine. The product was purified on a silica gel column using tetrahydrofuran as an eluent to obtain the pyridinium salt product 5;

[0151] The reaction formula is as follows:

[0152]

[0153] 5 mol fraction of pyridinium salt product 5, 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS–DMS) were added to a 250 mL three-necked flask and refluxed for 3 hours to complete the hydrosilylation reaction of the pyridinium salt product and P(MHS–DMS);

[0154] The reaction formula is as follows:

[0155]

[0156] Where: p is any integer between 1 and 11;

[0157] An excess of sodium dichloroisocyanurate dissolved in dimethyl sulfoxide solution was added to the product and reacted at room temperature for 5 hours to complete the chlorination reaction; the chlorinated product was purified by silica gel column using tetrahydrofuran as eluent to produce fluorine-containing pyridinium salt polychloramine bactericidal polymer polymer 5;

[0158] The reaction formula is as follows:

[0159]

[0160] Where: p is any integer between 1 and 11;

[0161] The infrared spectrum of polymer 5 is shown in the attached figure. Figure 3 shown.

[0162] Example 6 Preparation of Polymer 6

[0163] S1: Add 5 mol fraction of 6-perfluoropentyl-1-hexanol, 5 mol fraction of triethylamine, and 20 mol fraction of dichloromethane to a 100 mL three-necked flask equipped with a magnetic stirrer and a condenser, and place in an ice-water bath. Add 5 mol fraction of 3-bromopropionyl bromide dropwise to the flask and stir for 20 minutes. The reaction mixture is filtered to remove the precipitate, and the dichloromethane is removed by vacuum distillation to yield fluorinated bromoalkane 6.

[0164] The reaction formula is as follows:

[0165]

[0166] The reaction process of S2-S3 is the same as the reaction process of S2-S3 in Example 1.

[0167] S4: Add 8 mole fractions of fluorinated bromoalkane 6 to the above S3 product and reflux for 10 hours to complete the pyridinium salt reaction of the tertiary amine. The product is purified on a silica gel column using tetrahydrofuran as an eluent to obtain the pyridinium salt product 6. The reaction formula is as follows:

[0168]

[0169] S5: 5 mol fraction of pyridinium salt product 6, 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS-DMS) were added to a 250 mL three-necked flask and refluxed for 3 hours to complete the hydrosilylation reaction of the pyridinium salt product and P(MHS–DMS).

[0170] The reaction formula is as follows:

[0171]

[0172] Where: p is any integer between 1 and 11;

[0173] S6: Add an excess of sodium dichloroisocyanurate dissolved in dimethyl sulfoxide solution to the product of S5 and react at room temperature for 5 hours to complete the chlorination reaction; the chlorinated product is purified on a silica gel column using tetrahydrofuran as an eluent to produce a fluorine-containing pyridinium salt polychloramine bactericidal polymer, namely polymer 6.

[0174] The reaction formula is as follows:

[0175]

[0176] Where: p is any integer between 1 and 11;

[0177] Part 2 Bactericidal Effect of Polymers

[0178] Example 7 Preparation of Sterilization Layer

[0179] Add 50 mL of water, 0.01 mL of hydrochloric acid and 0.1 g of polymer 1 to a beaker, stir and hydrolyze for 30 minutes, add a 10 cm × 10 cm piece of cotton cloth, soak for 10 minutes, take out the cotton and put it into a 100 ° C oven for 20 minutes. A silicone rubber sterilization layer containing polymer 1 is formed on the cotton. The same method is used to prepare cotton with a silicone sterilization layer containing polymer 4; the thickness of the sterilization layer is 80-300 nm.

[0180] Add 50 mL of water, 0.5 mL of glacial acetic acid, and 1 g of polymer 2 obtained in Example 2 to a beaker, stir and hydrolyze for 20 minutes, add a silica mesoporous material with a pore size of 1 to 10 microns, and filter and remove the mesoporous material after 20 minutes; treat at 100°C for 30 minutes, and the hydrolyzed silane fungicide will shrink on the mesoporous material to form a fungicide polymer surface containing polymer 2. The same method is used to prepare a fungicide polymer surface containing polymer 5 in Example 5.

[0181] Example 8 Water contact angle test

[0182] The water contact angle test was performed on the sterilization layer containing polymers 1, 2, 4, and 5 prepared in Example 7. The test results are shown in Table 1:

[0183] Table 1 Water contact angle test

[0184]

[0185] The initial water contact angle test results of the sterilization layers containing different polymers show that the initial water contact angle value of the sterilization layer containing polymer 1 or polymer 2 is 78°, which is a typical contact angle produced by fluorine-containing and sulfur-containing compounds. Polymer 1 and polymer 2 contain heteroatom S, which causes the carbon-fluorine structure to reconstruct after occupying the surface, bending the upward CF segment downward, reducing the water contact angle, and reversing the bonded polar sterilization group to the water with high surface contact tension, which is conducive to direct contact between the sterilization group and the bacterial solution, and further enhancing the sterilization effect.

[0186] Polymer 4 also contains fluorine. The initial value of the water contact angle of the silicone rubber sterilization layer containing polymer 4 is 125°, which is a typical contact angle produced by fluorine-containing polymers, indicating that the carbon-fluorine structure is indeed on the outermost surface, thereby also carrying the sterilization structure bonded to the fluorine-containing structure to the outer surface. However, compared with polymer 1 or polymer 2, the fluorine-containing bromoalkane does not contain the heteroatom S, so its carbon-fluorine structure surface is not reconstructed, the CF segment angle is upward, and the contact angle is large.

[0187] The same method as in Example 8 was used to test the bactericidal performance of polymer 5 obtained in Example 5. The test showed that the initial water contact angle of the silicone rubber bactericidal layer containing polymer 5 prepared using polymer 5 was only 83°. Since F is a hydrophobic group, the initial water contact angle of polymer 5 not containing F is less than 90 degrees, indicating hydrophilicity.

[0188] Example 9 Sterilization Efficiency and Sterilization Stability Test

[0189] The 10 cm × 10 cm cotton cloth piece containing the sterilization layer of polymer 1 prepared in Example 7 was divided into two 2.5 cm × 2.5 cm cotton cloth pieces, and 25 uL of 10 6 ~10 7 A solution of Escherichia coli and Staphylococcus aureus containing 500 CFU / mL is sandwiched between two 2.5cm×2.5cm cotton cloth pieces, which can completely kill all pathogens after 1.5 minutes.

[0190] After being washed 50 times in a normal machine and then in contact with a bacterial solution for 45 minutes, the cotton fiber can still kill 99.99% of Escherichia coli and Staphylococcus aureus, proving its powerful bactericidal ability.

[0191] The mesoporous material containing the sterilization layer of polymer 2 was placed in a glass tube with a diameter of 1 cm and a height of 25 cm to prepare a filter column. The filtration concentration was 10 6 ×10 7 An aqueous solution of E. coli with a flow rate of 5 mL / min can kill 100% of the bacteria in the water.

[0192] It can be seen from the above experimental results that polymer 1 and polymer 2 exhibit good bactericidal effects on Staphylococcus aureus and Escherichia coli respectively under different bactericidal forms.

[0193] Polymers 4 and 5 were tested for their bactericidal ability in the same manner.

[0194] The 10cm×10cm cotton cloth piece containing the sterilization layer of polymer 4 was divided into two 2.5cm×2.5cm cotton cloth pieces, and 25uL of 10 6 ~10 7 A solution of Escherichia coli and Staphylococcus aureus containing 500 CFU / mL was sandwiched between two 2.5cm×2.5cm cotton cloth pieces. It took 8 minutes to completely kill the same number of Escherichia coli and Staphylococcus aureus.

[0195] The mesoporous material containing the sterilization layer of polymer 5 was placed in a glass tube with a diameter of 1 cm to prepare a filter column. The filtration concentration was 10 6 ×10 7For an aqueous solution of Escherichia coli containing 100 CFU / mL and a flow rate of 5 mL / min, the filling height of the mesoporous material in the glass tube needs to be extended to 50 cm to kill 100% of the bacteria in the water.

[0196] Polymers 1, 2, 4, and 5 all contain four halogenamine groups and one pyridine group, which means that the fungicide contains free halogen cationic monomers and chemically bonded halogenamine polymers N-Cl. Since the activity of the fungicide mainly comes from the N-Cl structure, the increase in the number of NX (X is a halogen) structures can enhance the synergistic effect and thus improve the bactericidal power. However, the bactericidal efficiency of NX (X is a halogen) is inversely proportional to the structural stability.

[0197] Halamine monomers are positively charged and exhibit strong oxidizing properties. They can react with certain active functional groups in microorganisms, destroying their enzymes and metabolism, thereby rendering the bacteria inactive. Halogen atoms are gradually consumed during the antibacterial process, and the NX bonds (X is a halogen) on the polymer are converted to NH bonds, gradually losing their antibacterial properties. However, when the NH bonds are converted back to NX bonds, their antibacterial properties can be restored.

[0198] Pyridinium salt fungicides mainly utilize pyridinium salts to contact the bacterial surface, changing the permeability of the cell wall and cell membrane, on the one hand causing the outflow of cell contents, and on the other hand penetrating deep into the bacteria to deform proteins, affecting the progress of enzymatic reactions, and ultimately causing bacterial death; however, the cationic center in the pyridinium salt fungicide and the NX (X is a halogen) site of the halamine fungicide play a synergistic role in the sterilization process: the positively charged nitrogen atoms in the pyridinium salt fungicide attract the negatively charged bacteria to the vicinity of the NX (X is a halogen) with high bactericidal ability through electrostatic action, killing the bacteria quickly. When there is no cationic nitrogen, the bacteria will contact the NX (X is a halogen) much more slowly through diffusion. Although bacteria are prone to develop resistance to cationic salts and antibiotics, the use of halamines avoids this problem.

[0199] Therefore, polymer 1, polymer 2, polymer 4 and polymer 5 all showed certain bactericidal effects when combined with different elements.

[0200] The biggest difference between polymer 5 and polymer 1, polymer 2 and polymer 4 is the lack of fluorine-containing brominated alkanes. Combined with the initial water contact angle test data in Example 8, it can be seen that polymer 5 does not exhibit good surface migration ability, so its bactericidal ability is obviously much weaker. In the bactericidal performance test, the mesoporous material filter column prepared using polymer 5 needs to be lengthened to 50 cm to kill 100% of the bacteria in the water, which also illustrates this problem. It also confirms that fluorine-containing brominated alkanes are conducive to the aggregation of bactericidal substances on the surface of the bactericidal layer, which has a significant effect on improving the bactericidal performance of the bactericidal polymer and has a better bactericidal effect.

[0201] Compared with polymers 1 and 2, polymer 4 does not introduce the sulfur element into the fluorinated bromoalkane, which cannot cause reconstruction of the bactericidal layer. When the bactericidal layer containing polymer 4 encounters the pathogen solution, the surface of the bactericidal layer is still a fluorocarbon polymer. Although this is conducive to the insertion of rigid fluorocarbon segments into bacteria, the highly ordered liquid crystals formed by the fluorocarbon polymer on the surface enhance the hydrophobicity and anti-adsorption properties of the bactericidal layer, which may hinder surface wetting and contact with bacteria.

[0202] In order to concentrate the bactericidal substances on the surface of the bactericidal layer to the greatest extent, enthalpy change can be used to prevent the surface from reconstructing when encountering a polar environment: after encountering a polar environment, the fluorocarbon polymer will flip to the sublayer, while the polar component flips to the top layer, eventually losing the low-tension surface phenomenon.

[0203] Taking the above problems into consideration, sulfur atoms are introduced into the CH and CF structures of fluorinated bromoalkanes to adjust the polymer's directional ability, flexibility, rigidity, hydrophilicity / hydrophobicity, steric hindrance, etc., so as to control the concentration and bactericidal efficiency of the bactericidal groups on the surface, as well as the hydrophilicity of the surface, thereby obtaining different structure-activity relationships.

[0204] The introduction of sulfur atoms into the CH and CF structures of polymers 1 and 2 in fluorinated bromoalkanes reconstructed the surface, reversing the polar bactericidal groups to the surface, improving the hydrophilicity of the polymers and the contact effect between the bactericidal layer containing the polymers and pathogens, promoting direct contact between the bactericidal groups in the bactericidal layer and the bacterial solution, and enhancing the bactericidal ability.

[0205] Example 11 Take-off angle test

[0206] Add 50 mL of water, 0.01 mL of hydrochloric acid and 0.1 g of polymer 6 into a beaker, stir and hydrolyze for 30 minutes, add a 10 cm × 10 cm piece of cotton cloth, soak for 10 minutes, take out the cotton and put it into a 100 ° C oven for 20 minutes. A silicone rubber sterilization layer containing polymer 6 will be formed on the cotton piece.

[0207] The cotton sheet containing polymer 1 and polymer 4 and the cotton sheet containing polymer 6 prepared in Example 7 were subjected to ADXPS to measure the distribution of different polymers at different depths of the cotton sheet.

[0208] ADXPS was used to measure the elemental composition and element valence at various depths within 10 nm of the surface of the silicone rubber sterilization layer cotton sheet containing polymer 1 and the silicone rubber sterilization layer cotton sheet containing polymer 6 by changing the take-off angle test. The distribution and valence of each element were qualitatively and quantitatively analyzed to obtain the concentration of sterilization groups at different depths. During the test, the N element only came from functional groups with sterilization ability, so the proportion of the N element was used to reflect the concentration of sterilization groups. The test results are shown in the following table.

[0209] Table 2 Atomic ratio of [N+] / [Si] at different photoelectron takeoff angles

[0210]

[0211] As can be seen from the table above, the ADXPS test results prove that the fluorinated halogenated alkanes with low surface tension can be used to enrich the highly polar bactericidal groups on the surface.

[0212] Comparing the atomic ratio of [N+] / [Si] at the same take-off angle, polymer 4 did not introduce any heteroatoms into the fluorine-containing haloalkane structure. After introducing heteroatoms S or O into the fluorine-containing haloalkane structure, it was found that the ratio was larger after introducing heteroatoms at the same take-off angle, indicating that the introduction of heteroatoms into the fluorine-containing structure is more conducive to the enrichment of bactericidal groups on the surface than the ordinary fluorine-containing haloalkane structure, thereby improving the bactericidal efficiency.

[0213] Comparing the atomic ratio of [N+] / [Si] in the cotton sheets containing polymer 1 and polymer 6, the introduction of sulfur atoms between the CH and CF groups in the fluorinated halogenated alkyl structure is more conducive to the enrichment of bactericidal groups on the surface. Therefore, polymer 1 has a stronger bactericidal effect in comparison.

[0214] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A fluorine-containing pyridinium salt polychloramine bactericidal polymer, characterized in that The fluorine-containing pyridinium salt polychloramine bactericidal polymer has the structure of the following formula (1): Wherein: X is a halogen; p is any integer between 1 and 11; n is any integer between 2 and 4; m is any integer between 2 and 4.

2. A fluorine-containing pyridinium salt polychloramine bactericidal polymer as claimed in claim 1, characterized in that The fluorine-containing pyridinium salt polychloramine bactericidal polymer has the structure of the following formula (1): Wherein: X is Cl or Br; p is any integer between 1 and 11; n is any integer between 2 and 4; m is any integer between 2 and 4.

3. A fluorine-containing pyridinium salt polychloramine bactericidal polymer as claimed in claim 1, characterized in that The fluorine-containing pyridinium salt polychloramine bactericidal polymer has the structure of the following formula (1): Wherein: X is a halogen; p is any integer between 1 and 11; n is 2 or 4; m is 4.

4. A fluorine-containing pyridinium salt polychloramine bactericidal polymer as claimed in claim 2, characterized in that The fluorine-containing pyridinium salt polychloramine bactericidal polymer has the structure of the following formula (1): Wherein: X is Cl or Br; p is any integer between 1 and 11; n is 2 or 4; m is 4.

5. A method for preparing a fluorine-containing pyridinium salt polychloramine bactericidal polymer according to any one of claims 1, 2, 3 or 4, characterized in that: S1. Preparation of fluorine-containing brominated alkane, the reaction formula is as follows: S2. Preparation of bactericidal precursor, the reaction formula is as follows: S3. The bactericidal precursor is bonded to 4-aminopyridine, and the reaction formula is as follows: S4: Preparation of pyridinium salt product, the reaction formula is as follows: S5: The pyridinium salt product is bonded to the hydrogenated silicone oil via a hydrosilation reaction: S6: Preparation of Fluorine-containing Pyridine Salt Polychloramine Bactericidal Polymers:

6. The method for preparing the fluorine-containing pyridinium salt polychloramine bactericidal polymer according to claim 5, wherein: In S1, azobisisobutyronitrile is added to 1-iodoperfluoropentane and 5-hexen-1-ol during the reaction process, and anhydrous ether and sodium dihydrobis(dimethoxyethoxy)aluminate are added respectively after the reaction is completed. To the obtained product, p-toluenesulfonyl chloride and sodium hydroxide are added, and then 4-bromobutanethiol is added and the mixture is heated under reflux to obtain a fluorine-containing bromoalkane; In S2: 2-aminobarbituric acid and allylsuccinic anhydride are added to the solution, dissolved, and then refluxed to obtain a bactericidal precursor; In S3: the bactericidal precursor and 4-aminopyridine are dissolved in a solution to complete the bonding between the bactericidal precursor and 4-aminopyridine; in S4: the fluorine-containing bromoalkane prepared in S1 is added to the product of S3 and refluxed to obtain a pyridinium salt product; In S5: the pyridinium salt product is dissolved in a solution, a catalyst and P(MHS–DMS) are added, and the mixture is refluxed to obtain the S5 product; in S6: a halogenating agent dissolved in a dimethyl sulfoxide solution is added to the S5 product to obtain a fluorine-containing pyridinium salt polychloramine bactericidal polymer.

7. The method for preparing a fluorine-containing pyridinium salt polychloramine bactericidal polymer according to claim 5, characterized in that: In S1, azobisisobutyronitrile was added to 1-iodoperfluoropentane and 5-hexen-1-ol in four portions at 80°C, and the mixture was reacted for 8 hours before vacuum distillation. Anhydrous ether and sodium dihydrobis(dimethoxyethoxy)aluminate were then added, reacted at room temperature for 3 hours, and purified. To the obtained product, p-toluenesulfonyl chloride and sodium hydroxide were added, and the mixture was heated under reflux for 4 hours before purification. 4-bromobutanethiol was added to the purified product, and the mixture was heated under reflux for 6 hours to obtain a fluorine-containing bromoalkane after purification. In S2, the solution was anhydrous DMSO, 2-aminobarbituric acid and allylsuccinic anhydride were dissolved in anhydrous DMSO, refluxed for 4 hours, and distilled after the reaction to obtain a bactericidal precursor. In S3: the solution is a mixed solution of EDC and sNHS, the bactericidal precursor and 4-aminopyridine are dissolved in the mixed solution of EDC and sNHS, and the mixture is reacted at room temperature for 10 hours to complete the bonding between the bactericidal precursor and 4-aminopyridine; In S4: the fluorine-containing bromoalkane prepared in S1 is added to the product of S3 and refluxed for 10 hours, and the pyridinium salt product is obtained after purification; In S5, the solution is anhydrous tetrahydrofuran, and the catalyst is chloroplatinic acid catalyst; the pyridinium salt product is dissolved in anhydrous tetrahydrofuran, chloroplatinic acid catalyst and P(MHS-DMS) are added, and the reaction is refluxed for 3 hours to obtain the S5 product; In S6: a halogenating agent dissolved in a dimethyl sulfoxide solution is added to the product of S5, and the mixture is reacted at room temperature for 5 hours, and the fluorine-containing pyridinium salt polychloramine bactericidal polymer is purified.

8. The method for preparing a fluorine-containing pyridinium salt polychloramine bactericidal polymer according to claim 7, wherein: In S1, 0.025 mol fraction of azobisisobutyronitrile was added four times to 5 mol fraction of 1-iodoperfluoropentane and 7.5 mol fraction of 5-hexen-1-ol at 80° C., and the mixture was reacted for 8 hours before vacuum distillation; 15 mol fraction of anhydrous ether and 6.5 mol fraction of sodium dihydrobis(dimethoxyethoxy)aluminate were added respectively, and the mixture was reacted at room temperature for 3 hours, followed by purification; 7.5 mol fraction of p-toluenesulfonyl chloride and 0.5 mol fraction of sodium hydroxide were added to the obtained product, and the mixture was heated under reflux for 4 hours before purification; 7.5 mol fraction of 4-bromobutanethiol was added to the purified product, and the mixture was heated under reflux for 6 hours, and the fluorine-containing bromoalkane was obtained after purification; In S2: 5 mol fraction of 2-aminobarbituric acid and 5 mol fraction of allylsuccinic anhydride are dissolved in 20 mol fraction of anhydrous DMSO, refluxed for 4 hours, and distilled after reaction to obtain a bactericidal precursor; In S3: 5 mol fraction of the bactericidal precursor and 5 mol fraction of 4-aminopyridine are dissolved in a mixed solution of 15 mol fraction of EDC and 30 mol fraction of sNHS, and reacted at room temperature for 10 hours to complete the bonding of the bactericidal precursor and 4-aminopyridine; In S4: adding 8 mole fractions of the fluorine-containing bromoalkane prepared in S1 to the product of S3, reflux for 10 hours, and purify to obtain the pyridinium salt product; In S5: 5 mol fraction of the pyridinium salt product was dissolved in 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS–DMS) were added, and the mixture was refluxed for 3 hours to obtain the S5 product; In S6: a halogenating agent dissolved in an excess amount of dimethyl sulfoxide solution is added to the product of S5, and the mixture is reacted at room temperature for 5 hours. After purification, a fluorine-containing pyridinium salt polychloramine bactericidal polymer is obtained.

9. The method for preparing a fluorine-containing pyridinium salt polychloramine bactericidal polymer according to claim 8, characterized in that: In S1, 0.025 mole fraction of azobisisobutyronitrile was added four times to 5 mole fraction of 1-iodoperfluoropentane and 7.5 mole fraction of 5-hexen-1-ol at 80° C., and the mixture was reacted for 8 hours and then distilled under reduced pressure; 15 mole fraction of anhydrous ether and 6.5 mole fraction of sodium dihydrobis(dimethoxyethoxy)aluminate were added respectively, and the mixture was reacted at room temperature for 3 hours, extracted with dichloromethane, dried over anhydrous MgSO4, and distilled under reduced pressure; 7.5 mole fraction of p-toluenesulfonyl chloride and 0.5 mole fraction of sodium hydroxide were added to the obtained product, and the mixture was heated under reflux for 4 hours and then purified. 7.5 mole fraction of 4-bromobutanethiol was added to the purified product, and the mixture was heated under reflux for 6 hours. 50 mole fraction of ether was added to dissolve the mixture, and the mixture was purified by passing through a short silica gel column using ether as an eluent to obtain a fluorine-containing bromoalkane; In S2: 5 mol fraction of 2-aminobarbituric acid and 5 mol fraction of allylsuccinic anhydride are dissolved in 20 mol fraction of anhydrous DMSO, refluxed for 4 hours, and distilled after reaction to obtain a bactericidal precursor; In S3: 5 mol fraction of the bactericidal precursor and 5 mol fraction of 4-aminopyridine are dissolved in a mixed solution of 15 mol fraction of EDC and 30 mol fraction of sNHS, and reacted at room temperature for 10 hours to complete the bonding of the bactericidal precursor and 4-aminopyridine; In S4: 8 mol fractions of the fluorine-containing bromoalkane prepared in S1 are added to the product of S3, and the mixture is refluxed for 10 hours. The product is purified on a silica gel column using tetrahydrofuran as an eluent to obtain a pyridine salt product; In S5: 5 mol fraction of the pyridinium salt product was dissolved in 15 mol fraction of anhydrous tetrahydrofuran, 0.01 mol fraction of chloroplatinic acid catalyst and 5 mol fraction of P(MHS–DMS) were added, and the mixture was refluxed for 3 hours to obtain the S5 product; In S6: a halogenating agent dissolved in an excess of dimethyl sulfoxide solution is added to the product of S5, and the mixture is reacted at room temperature for 5 hours. The product is purified by silica gel column using tetrahydrofuran as an eluent to obtain a fluorine-containing pyridinium salt polychloramine bactericidal polymer.

10. Use of the fluorine-containing pyridinium salt polychloramine bactericidal polymer according to any one of claims 1, 2, 3 or 4 in the preparation of bactericidal cotton sheets and filter columns.

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