Isobutylene-based cationic salt polymer, its preparation method and use, antibacterial polymer material

Abstract

The present invention relates to the field of polymeric materials and discloses an isobutylene-based cation salt ionic polymer, and its preparation and use. The polymer comprises a structure represented by formula (2) and / or formula (3), optionally including a structural unit A having a structure represented by formula (1), a structural unit B having a structure represented by formula (4), and a structural unit C having a structure represented by formula (5). By containing cation salt functional groups in both the side groups and the main chain of the polymer, the polymer has a high degree of polyionization and can be used as an antibacterial agent to prepare antibacterial polymeric materials such as antibacterial plastics, antibacterial rubber, antibacterial fibers, and antibacterial paints. [Formula 1] TIFF2025535581000053.tif68169 (Q is [chemical 2] TIFF2025535581000054.tif33169 )

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of Chinese Patent Applications Nos. 202211411837.6, 202211415126.6, 202211411836.1, and 202211412278.0, filed on November 11, 2022, November 11, 2022, and November 11, 2022, the contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of antibacterial functional polymeric materials, in particular to an isobutylene-based cationic salt ionic polymer, and its preparation method and use, antibacterial polymeric materials. [Background technology]

[0003] There are two types of commercially available isobutylene-based random copolymers: an unsaturated copolymer of isobutylene and isoprene, and a saturated copolymer of isobutylene and p-methylstyrene. When both copolymers are subjected to a bromination reaction, brominated modified products, brominated isobutylene-isoprene rubber (BIIR) and brominated isobutylene-p-methylstyrene rubber (BIMS), are obtained. The main application areas of these two products are airtight layers in tires and medical stoppers. Commercially available BIIR and BIMS have high molecular weights (weight average molecular weight M w A rubber-based elastomer product characterized by a low content of copolymerized functional monomers (a molecular weight of 500,000 or more), and generally has a mole fraction of isoprene of less than 3%, a mole fraction of p-methylstyrene of less than 5%, and a mole fraction of functional bromine of less than 1.5% in the copolymer.

[0004] Isobutylene-based ionic polymers in the prior art are generally produced using commercially available BIIR or BIMS as the base rubber. For example, see Synthesis and characterization of isobutylene-based ammonium and phosphonium bromide ionomers (Macromolecules, 2004, 37, 7477-7483), Quaternary ammonium BIMS ionomers (Presented at the 163 rdThe Technical Meeting of the Rubber Division, American Chemical Society, San Francisco, California, April 28-30, 2003, discloses that BIIR or BIMS rubbers are melt-blended and reacted with alkylamines, alkylphosphines, imidazoles, etc. in a Banbury mixer at 130°C. This process induces nucleophilic substitution of the allyl bromo functional groups in BIIR or the benzyl bromo functional groups in BIMS, resulting in ionic polymers such as ammonium, phosphonium, and imidazole salts. Alternatively, for example, in "An imidazolium-functionalized isobutylene polymer having improved mechanical and barrier properties: synthesis and characterization" (J. APPL. POLYM. SCI. 2012, DOI: 10.1002 / APP. 38458), the BIIR or BIMS product is redissolved in an organic solvent and the ionization reaction is carried out for a long period of time. BIIR and BIMS rubbers have a low content of copolymerized functional monomers, limiting the range of ionization. The molar content of ionic salts is generally less than 1%, making it difficult to expand their application. Therefore, they are often used only as ionic rubbers in conventional vulcanized rubber products such as CN112135848A. Furthermore, these ionic rubber elastomers are difficult to blend directly with resins, and specific dynamic mixing vulcanization techniques are required to prepare rubber-plastic composites.

[0005] Bacteria, fungi, and viruses have traditionally been pathogenic microorganisms that threaten human life and health. Due to the increasing drug resistance of pathogens and the continuous emergence of new pathogens, new antibacterial treatments are urgently needed. One important way to block the spread of pathogens in the environment is to apply antibacterial / antiviral coatings to object surfaces to prevent the growth of pathogenic microorganisms. Therefore, antibacterial polymeric materials, such as antibacterial fibers, antibacterial plastics, antibacterial rubber, and antibacterial paints, have emerged and are increasingly used in daily life.

[0006] Among small molecule organic antibacterial agents, cationic salt compounds, due to their strong positive charge, are less likely to develop resistance in pathogenic microorganisms and are therefore widely used as antibacterial agents, bactericides, surfactants, and antistatic agents. Examples include quaternary ammonium salts, quaternary phosphonium salts, guanidine salts, imidazole salts, pyridine salts, and pyrimidine salts. Quaternary ammonium salts, in particular, are widely used as bactericides and bacteriostatic agents in areas such as daily laundry, medical disinfection, aquaculture, and industrial circulating water algae control. For example, common compounds such as benzalkonium chloride and benzalkonium bromide have excellent bactericidal and bacteriostatic effects against bacteria, including Gram-negative and Gram-positive bacteria. However, small molecule antibacterial agents are released into the environment, which means they are easily lost and have a short duration of action, which can cause environmental pollution. Furthermore, the stronger the antibacterial activity, the more toxic they are, potentially affecting the health of humans and animals. Furthermore, small molecule organic antibacterial agents generally lack high-temperature resistance, making them difficult to withstand high-temperature processing of polymeric materials and prone to migration and release within the material. Therefore, metal-type inorganic nano-antibacterial agents remain the mainstream in the field of polymeric materials, but their drawbacks include the release of metal toxins into the environment to kill bacteria, their inability to withstand washing, and their short duration of action, meaning that the antibacterial properties of the material decrease over time.

[0007] In recent years, research into the preparation of polymeric cationic salt antibacterial agents has been intensively pursued, but the complex and costly preparation methods have made large-scale industrial production and practical application difficult. For example, methods include immersing polymeric materials or products in strong oxidizing solutions, or subjecting the surface of polymeric materials to high-energy irradiation, ozone treatment, or plasma treatment to generate active centers on the surface and initiate graft copolymerization of quaternary ammonium salt monomers. These surface treatment methods are prone to decomposition and crosslinking of the polymeric surface, which can affect or destroy the mechanical properties of the material. Furthermore, the grafting amount is unstable and reproducible. Alternatively, when small-molecule quaternary ammonium salt organic compounds are grafted onto specific fillers via chemical reaction and then added to the polymeric material, the loading amount is unstable and the dispersion of the filler in the polymeric material often affects the antibacterial effect. Alternatively, quaternary ammonium salts can be grafted onto copolymerizable monomers that can participate in polymer synthesis, and antibacterial polymer materials can be directly prepared by copolymerization. However, this complicates the polymer preparation process, increasing production costs, and also affects the polymer polymerization reaction, making practical application difficult. Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides an isobutylene-based cationic salt ionic polymer, and a preparation method and use thereof, to overcome the prior art problem of isobutylene-based copolymers having low functional group content and very limited ionization degree, which limits the application fields of isobutylene-based cationic salt polymers. This isobutylene-based cationic salt ionic polymer has a polymer backbone composed of main structural units provided by isobutylene and functional structural units provided by alkylstyrene, and contains cationic salt functional groups in both the side groups and the main chain of the polymer, resulting in a satisfactory high degree of ionization. As an antibacterial agent, it can be used to prepare antibacterial polymer materials with stable, durable, safe, and low toxicity, such as antibacterial plastics, antibacterial rubber, antibacterial fibers, and antibacterial paints, and can effectively inhibit and kill bacteria, fungi, and pathogens. [Means for solving the problem]

[0009] In order to achieve the above object, a first aspect of the present invention is an isobutylene-based cation salt ionic polymer, the polymer comprising structural units A, B, and C, The structural unit A has a structure represented by formula (2) and / or formula (3) and, optionally, a structure represented by formula (1), the structural unit B has a structure represented by formula (4), and the structural unit C has a structure represented by formula (5). [ka] (wherein R1 is C1-C4 alkylene, R2 is C1-C4 alkyl, Q is [ka] and Here, R3, R4, and R5 are each independently C1 to C 20 Straight chain alkyl, C1-C20 Branched alkyl, or C6-C 20 is an aryl of R6, R7, and R8 are each independently C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl, or C6-C 10 is an aryl of R9 is hydrogen, C1 to C 20 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, or C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6~C 10 and n is an integer of 0 to 5. R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a halogen atom, or C1 to C 20 Straight chain alkyl, C1-C 20 branched alkyl, nitro, amino, or cyano; X is Cl or Br.

[0010] A second aspect of the present invention is a method for preparing an isobutylene-based cationic salt ionic polymer, comprising: The preparation method comprises: Step (1) of dissolving a polymer in an organic solvent to obtain a polymer solution, and adding a halogen to the polymer solution to perform a halogenation reaction to obtain a halogenated polymer solution; and (2) adding at least one of a tertiary amine compound, a tertiary phosphine compound, an imidazole compound, and a pyridine compound to the halogenated polymer solution to carry out an ionization reaction, thereby obtaining the isobutylene-based cation salt ionic polymer; the polymer is a random copolymer of isobutylene and alkylstyrene; The halogenation reaction is carried out under irradiation with visible light, and the visible light is emitted in pulsed mode.

[0011] A third aspect of the present invention provides an isobutylene-based cationic salt ionic polymer prepared by the above preparation method.

[0012] A fourth aspect of the present invention provides the use of the above-mentioned isobutylene-based cationic salt ionic polymer as an antibacterial agent.

[0013] A fifth aspect of the present invention provides the use of the isobutylene-based cationic salt ionic polymer described above in inhibiting and killing at least one of bacteria, fungi, and viruses.

[0014] A sixth aspect of the present invention provides an antibacterial polymer material comprising the above-mentioned isobutylene-based cation salt ionic polymer. [Effects of the Invention]

[0015] According to the above technical solutions, the isobutylene-based cationic salt ionic polymer according to the present invention, and its preparation method and use, antibacterial polymer material, can achieve the following beneficial effects:

[0016] The isobutylene-based cationic salt ionic polymer according to the present invention comprises a main structural unit provided by isobutylene and a functional structural unit provided by alkylstyrene, contains a high content of cationic salt functional groups, and has a satisfactory higher degree of ionization. As an antibacterial agent, it can be used to prepare stable, durable, safe, and low-toxic antibacterial polymeric materials such as antibacterial plastics, antibacterial rubber, antibacterial fibers, and antibacterial paints, and can effectively inhibit and kill bacteria, fungi, pathogens, etc. [Brief explanation of the drawings]

[0017] [Figure 1a]1 is a 1H-NMR spectrum of brominated isobutylene-p-methylstyrene copolymer XP-I-1 in Example I-1. [Figure 1b] 1 is a 1H-NMR spectrum of an isobutylene-based quaternary ammonium salt ionic polymer AI-1 in Example I-1. [Figure 1c] 1 is a thermal weight loss map of isobutylene-p-methylstyrene copolymer PI-1. [Figure 1d] 1 is a thermal weight loss map of brominated isobutylene-p-methylstyrene copolymer XP-I-1. [Figure 1e] 1 is a thermal weight loss map of the isobutylene-based quaternary ammonium salt ionic polymer AI-1 in Example I-1. [Figure 2a] 1 is a 1H-NMR spectrum of brominated isobutylene-p-methylstyrene copolymer XP-II-1 in Example II-1. [Figure 2b] 1 is a 1H-NMR spectrum of an isobutylene-based quaternary phosphonium salt ionic polymer A-II-1 in Example II-1. [Figure 2c] 1 is a thermal weight loss map of isobutylene-p-methylstyrene copolymer P-II-1. [Figure 2d] 1 is a thermal weight loss map of brominated isobutylene-p-methylstyrene copolymer XP-II-1. [Figure 2e] 1 is a thermal weight loss map of an isobutylene-based quaternary phosphonium salt ionic polymer in Example II-1. [Figure 3a] 1 is a 1H-NMR spectrum of brominated isobutylene-p-methylstyrene copolymer XP-III-1 in Example III-1. [Figure 3b] 1 is a 1H-NMR spectrum of an isobutylene-based imidazole salt ionic polymer A-III-1 in Example III-1. [Figure 3c] 1 is a thermal weight loss map of isobutylene-p-methylstyrene copolymer P-III-1. [Figure 3d]1 is a thermal weight loss map of brominated isobutylene-p-methylstyrene copolymer XP-III-1 in Example III-1. [Figure 3e] 1 is a thermal weight loss map of an isobutylene-based imidazole salt ionic polymer A-III-1 in Example III-1. [Figure 4a] 1 is a 1H-NMR spectrum of brominated isobutylene-p-methylstyrene copolymer XP-IV-1 in Example IV-1. [Figure 4b] 1 is a 1H-NMR spectrum of an isobutylene-based pyridine salt ionic polymer A-IV-1 in Example IV-1. [Figure 4c] 1 is a thermal weight loss map of isobutylene-p-methylstyrene copolymer P-IV-1. [Figure 4d] 1 is a thermal weight loss map of brominated isobutylene-p-methylstyrene copolymer XP-IV-1 in Example IV-1. [Figure 4e] 1 is a thermal weight loss map of an isobutylene-based pyridine salt ionic polymer A-IV-1 in Example IV-1. DETAILED DESCRIPTION OF THE INVENTION

[0018] The endpoints of the ranges and any values ​​disclosed herein should be understood not to be limited to the exact range or value, but to include values ​​close to those ranges or values. With respect to numerical ranges, the endpoints of each range, the endpoints of each range and individual dot values, and the individual dot values ​​can be combined to obtain one or more new numerical ranges, which are considered to be specifically disclosed herein. A first aspect of the present invention is an isobutylene-based cation salt ionic polymer, the polymer comprising structural unit A, structural unit B, and structural unit C;

[0019] The structural unit A has a structure represented by formula (2) and / or formula (3) and, optionally, a structure represented by formula (1), the structural unit B has a structure represented by formula (4), and the structural unit C has a structure represented by formula (5). [ka] (wherein R1 is C1-C4 alkylene, R2 is C1-C4 alkyl, Q is [ka] and Here, R3, R4, and R5 are each independently C1 to C 20 Straight chain alkyl, C1-C 20 Branched alkyl, or C6-C 20 is an aryl of R6, R7, and R8 are each independently C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl, or C6-C 10 is an aryl of R9 is hydrogen, C1 to C 20 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, or C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6~C 10 and n is an integer of 0 to 5. R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a halogen atom, or C1 to C 20 Straight chain alkyl, C1-C20 branched alkyl, nitro, amino, or cyano; X is Cl or Br.

[0020] In the present invention, the isobutylene-based cation salt ionic polymer comprises a polymer skeleton consisting of a main structural unit provided by isobutylene and a functional structural unit provided by alkylstyrene. By introducing cation salt functional groups into both the side groups of the alkylstyrene units and the main chain of the polymer, the polymer has a satisfactory high degree of ionization and can be used as an antibacterial agent to prepare highly effective, stable, durable, safe and low-toxicity antibacterial polymer materials such as antibacterial plastics, antibacterial rubber, antibacterial fibers and antibacterial paints, and can also effectively inhibit and kill bacteria, fungi and pathogens.

[0021] In one particular embodiment of the present invention, R1 is methylene or ethylene, preferably methylene; R2 is methyl or ethyl, preferably methyl; and R3, R4, and R5 are each independently C1 to C6. 18 or C6 to C9 aryl, preferably methyl, C8 to C 16 or phenyl, and X is Br.

[0022] In one particular embodiment of the present invention, R1 is methylene or ethylene, preferably methylene; R2 is methyl or ethyl, preferably methyl; R6, R7, and R8 are each independently C1-C8 straight chain alkyl, C5-C8 cycloalkyl, C6-C8 aryl, preferably C1-C8 straight chain alkyl, cyclopentyl, cyclohexyl, or phenyl; and X is Br.

[0023] In one particular embodiment of the invention, R1 is methylene or ethylene, preferably methylene, R2 is methyl or ethyl, preferably methyl, and R9 is hydrogen, C1-C 18 Straight chain alkyl, preferably hydrogen, C1-C 16is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, a C1-C5 linear alkyl, a C1-C5 branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6-C8 aryl, and n is an integer of 0 to 3, preferably hydrogen, C1-C 16 R3, R4, and R5 are each independently hydrogen, a halogen atom, a C1-C4 linear alkyl, hydroxy, nitro, cyano, amino, or phenyl, and X is Br.

[0024] In one particular embodiment of the invention, R1 is methylene or ethylene, preferably methylene, R2 is methyl or ethyl, preferably methyl, and R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, halogen, C1 to C 15 Straight chain alkyl, C1-C 15 branched alkyl, nitro, amino, or cyano, preferably hydrogen, halogen, C1-C 10 is a straight chain alkyl, amino, or cyano, and X is Br.

[0025] According to the present invention, the content of the cation salt functional group is 1.5 to 35 mol % based on the total molar amount of the polymer.

[0026] In one specific embodiment of the present invention, when the content of the group in the polymer is controlled to satisfy the above range, the antibacterial properties of the polymer material containing the polymer can be further improved.

[0027] Furthermore, based on the total molar amount of the polymer, in one particular embodiment of the present invention, the content of the group is 2.5 to 25 mol %.

[0028] According to the present invention, based on the total molar amount of the polymer, the content of side group benzyl cation salt functional groups is 1 to 20 mol %, and the content of main chain tertiary carbocation salt functional groups is 0.5 to 15 mol %.

[0029] In the present invention, when the contents of the side chain cation salt functional groups and the main chain tertiary carbocation salt functional groups in the polymer satisfy the above ranges, the polymer has more efficient bactericidal and bacteriostatic properties.

[0030] In the present invention, the main chain tertiary carbocation salt functional group means that the cation salt functional group is on the main chain of the alkylstyrene, and includes the cation salt functional group on the alkylstyrene main chain in the structural unit represented by formula (2) and the structural unit represented by formula (3). In the present invention, the content of the main chain cation salt functional group is the total content of the cation salt functional group in the structural unit represented by formula (2) and the content of the cation salt functional group on the main chain in the structure represented by formula (3).

[0031] In the present invention, the side group cation salt functional group means that the cation salt functional group is on the side group of the alkylstyrene, and includes the cation salt functional group on the alkylstyrene side group in the structural unit represented by formula (1) and the structural unit represented by formula (3). In the present invention, the content of the side group benzyl cation salt functional group is the total content of the cation salt functional group in the structural unit represented by formula (1) and the cation salt functional group in the side group of the structural unit represented by formula (3).

[0032] Furthermore, based on the total molar amount of the polymer, the content of side benzyl cation salt functional groups is 1.5 to 15 mol %, and the content of main chain tertiary carbocation salt functional groups is 1 to 10 mol %.

[0033] According to the present invention, the content of the structural unit A is 1 to 20 mol %, the content of the structural unit B is 0.5 to 10 mol %, and the content of the structural unit C is 75 to 97 mol %.

[0034] In the present invention, the isobutylene-based cation salt ionic polymer comprises a structural unit A represented by formula (3), which comprises both a side group cation salt functional group and a main chain cation salt functional group, so that the total content of the cation salt functional group in the isobutylene cation salt ionic polymer is higher than the content of the structural unit A.

[0035] In the present invention, since the isobutylene-based cationic salt ionic polymer has a high content of structural unit A, more cationic salt functional groups can be introduced into the polymer, and the final polymer has a higher content of cationic salt functional groups. As a result, this polymer can be used as an antibacterial agent to prepare antibacterial polymer materials with stable and durable antibacterial properties, as well as safe and low toxicity, such as antibacterial plastics, antibacterial rubber, antibacterial fibers, and antibacterial paints, and can also effectively inhibit and kill bacteria, fungi, pathogens, etc.

[0036] Furthermore, based on the total molar amount of the polymer, the content of the structural unit A is 2 to 15 mol %, the content of the structural unit B is 1 to 5 mol %, and the content of the structural unit C is 80 to 95 mol %.

[0037] According to the present invention, the thermal decomposition temperature of the isobutylene-based cation salt ionic polymer is 150 to 550°C.

[0038] According to the present invention, the 5 wt % thermal weight loss temperature of the isobutylene-based cationic salt ionic polymer is 170° C. or higher.

[0039] In the present invention, the isobutylene-based cationic salt ionic polymer has a high thermal decomposition temperature and a high 5 wt% thermal weight loss temperature, which meets the requirements for the thermal processing of polymer materials. Therefore, it can be directly combined with polymer materials as an antibacterial agent and used to prepare antibacterial polymer materials such as antibacterial plastics, antibacterial rubber, antibacterial fibers, and antibacterial paints.

[0040] Furthermore, the thermal decomposition temperature of the isobutylene-based cationic salt ionic polymer is 180 to 500°C.

[0041] Furthermore, the 5 wt % thermal weight loss temperature of the isobutylene-based cationic salt ionic polymer is 180° C. or higher. Specific Embodiment I

[0042] The isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary ammonium salt ionic polymer, and the polymer comprises a structural unit A, a structural unit B, and a structural unit C; The structural unit A has a structure represented by formula (2-1) and / or formula (3-1) and, optionally, a structure represented by formula (1-1), the structural unit B has a structure represented by formula (4-1), and the structural unit C has a structure represented by formula (5-1). [ka] (wherein R1 is C1-C4 alkylene, R2 is C1-C4 alkyl, and R3, R4, and R5 are each independently C1-C 20 Straight chain alkyl, C1-C 20 Branched alkyl, or C6-C 20 and X is Cl or Br. Furthermore, R1 is methylene or ethylene, R2 is methyl or ethyl, and R3, R4, and R5 are each independently C1 to C 18 or a C6 to C9 aryl, and X is Br. Furthermore, R1 is methylene, R2 is methyl, and R3, R4, and R5 are each independently methyl, C8 to C 16 or phenyl, and X is Br.

[0043] According to the present invention, the content of the quaternary ammonium salt functional group is 1.5 to 35 mol % based on the total molar amount of the polymer. Furthermore, the content of the quaternary ammonium salt functional group is 2.5 to 25 mol % based on the total molar amount of the polymer.

[0044] According to the present invention, based on the total molar amount of the polymer, the content of side group benzyl quaternary ammonium salt functional groups is 1 to 20 mol %, and the content of main chain tertiary carbon quaternary ammonium salt functional groups is 0.5 to 15 mol %.

[0045] Furthermore, based on the total molar amount of the polymer, the content of side benzyl quaternary ammonium salt functional groups is 1.5 to 15 mol %, and the content of main chain tertiary carbon quaternary ammonium salt functional groups is 1 to 10 mol %.

[0046] According to the present invention, the content of the structural unit A is 1 to 20 mol %, the content of the structural unit B is 0.5 to 10 mol %, and the content of the structural unit C is 75 to 97 mol %.

[0047] Furthermore, based on the total molar amount of the polymer, the content of the structural unit A is 2 to 15 mol %, the content of the structural unit B is 1 to 5 mol %, and the content of the structural unit C is 80 to 95 mol %.

[0048] According to the present invention, the thermal decomposition temperature of the isobutylene-based quaternary ammonium salt ionic polymer is 150 to 500°C. According to the present invention, the 5 wt % thermal weight loss temperature of the isobutylene-based quaternary ammonium salt ionic polymer is 170° C. or higher.

[0049] In the present invention, the isobutylene-based quaternary ammonium salt ionic polymer has a high thermal decomposition temperature and a high 5 wt% thermal weight loss temperature, so it meets the requirements for thermal processing of polymer materials. It can be directly combined with polymer materials as an antibacterial agent and used to prepare antibacterial polymer materials such as antibacterial plastics, antibacterial rubber, antibacterial fibers, and antibacterial paints.

[0050] Furthermore, the thermal decomposition temperature of the isobutylene-based quaternary ammonium salt ionic polymer is 180 to 450°C. Furthermore, the 5 wt % thermal weight loss temperature of the isobutylene-based quaternary ammonium salt ionic polymer is 180° C. or higher. Specific Embodiment II

[0051] The isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary phosphonium salt ionic polymer, and the polymer has structural units A, B, and C;

[0052] The structural unit A has a structure represented by at least one of formula (2-2) and / or formula (3-2), and optionally a structure represented by formula (1-2), the structural unit B has a structure represented by formula (4-2), and the structural unit C has a structure represented by formula (5-2). [ka] (wherein R1 is C1-C4 alkylene, R2 is C1-C4 alkyl, and R6, R7, and R8 are each independently C1-C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl, or C6-C 10 and X is Cl or Br; Furthermore, R1 is methylene or ethylene, R2 is methyl or ethyl, and R3, R4, and R5 are each independently C1 to C 18 or a C6 to C9 aryl, and X is Br. Furthermore, R1 is methylene, R2 is methyl, R6, R7, and R8 are each independently a C1-C8 linear alkyl, cyclopentyl, cyclohexyl, or phenyl, and X is Br.

[0053] According to the present invention, the content of the quaternary phosphonium salt functional group is 1.5 to 23 mol % based on the total molar amount of the polymer.

[0054] Furthermore, the content of the quaternary phosphonium salt functional group is 3 to 18 mol % based on the total molar amount of the polymer.

[0055] According to the present invention, based on the total molar amount of the polymer, the content of the side group benzyl quaternary phosphonium salt functional group is 1 to 15 mol %, and the content of the main chain tertiary carbon quaternary phosphonium salt functional group is 0.5 to 8 mol %.

[0056] Furthermore, based on the total molar amount of the polymer, the content of side group benzyl quaternary phosphonium salt functional groups is 2 to 13 mol %, and the content of main chain tertiary carbon quaternary phosphonium salt functional groups is 1 to 5 mol %.

[0057] According to the present invention, based on the total molar amount of the polymer, the content of the structural unit A is 1 to 20 mol %, the content of the structural unit B is 0.5 to 10 mol %, and the content of the structural unit C is 75 to 97 mol %.

[0058] Furthermore, based on the total molar amount of the polymer, the content of the structural unit A is 2 to 15 mol %, the content of the structural unit B is 1 to 5 mol %, and the content of the structural unit C is 80 to 95 mol %.

[0059] According to the present invention, the thermal decomposition temperature of the isobutylene-based quaternary phosphonium salt ionic polymer is 150 to 500°C.

[0060] According to the present invention, the 5 wt % thermal weight loss temperature of the isobutylene-based quaternary phosphonium salt ionic polymer is 200° C. or higher.

[0061] Furthermore, the thermal decomposition temperature of the isobutylene-based quaternary phosphonium salt ionic polymer is 200 to 450°C.

[0062] Furthermore, the isobutylene-based quaternary phosphonium salt ionic polymer has a 5 wt % thermal weight loss temperature of 220° C. or higher. Specific Embodiment III

[0063] In one particular embodiment of the invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based imidazole salt ionic polymer, the polymer comprising structural unit A, structural unit B, and structural unit C; The structural unit A has a structure represented by at least one of formula (2-3) and / or formula (3-3), and optionally a structure represented by formula (1-3), the structural unit B has a structure represented by formula (4-3), and the structural unit C has a structure represented by formula (5-3). [ka] (wherein R1 is C1-C4 alkylene, R2 is C1-C4 alkyl, and R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a halogen atom, or C1 to C 20 Straight chain alkyl, C1-C 20 and X is Cl or Br. Furthermore, R1 is methylene or ethylene, R2 is methyl or ethyl, and R9 is hydrogen, C1-C 18 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, a C1-C5 linear alkyl, a C1-C5 branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6-C8 aryl, n is an integer of 0 to 3, and X is Br. Furthermore, R1 is methylene, R2 is methyl, and R9 is hydrogen, C1 to C 16is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, a C1-C4 linear alkyl, hydroxy, nitro, amino, cyano, or phenyl, and X is Br.

[0064] According to the present invention, the content of imidazole salt functional groups is 1.5 to 23 mol % based on the total molar amount of the polymer.

[0065] Furthermore, the content of imidazole salt functional groups is 3 to 18 mol % based on the total molar amount of the polymer.

[0066] According to the present invention, based on the total molar amount of the polymer, the content of side benzylimidazole salt functional groups is 1 to 15 mol %, and the content of main chain tertiary carbon imidazole salt functional groups is 0.5 to 8 mol %.

[0067] Furthermore, based on the total molar amount of the polymer, the content of side benzylimidazole salt functional groups is 2 to 13 mol %, and the content of main chain tertiary carbon imidazole salt functional groups is 1 to 5 mol %.

[0068] According to the present invention, based on the total molar amount of the polymer, the content of the structural unit A is 1 to 20 mol %, the content of the structural unit B is 0.5 to 10 mol %, and the content of the structural unit C is 75 to 97 mol %.

[0069] Furthermore, based on the total molar amount of the polymer, the content of the structural unit A is 2 to 15 mol %, the content of the structural unit B is 1 to 5 mol %, and the content of the structural unit C is 80 to 95 mol %.

[0070] According to the present invention, the thermal decomposition temperature of the isobutylene imidazole salt ionic polymer is 150 to 550°C.

[0071] According to the present invention, the 5 wt % thermal weight loss temperature of the isobutylene-based imidazole salt ionic polymer is 200° C. or higher.

[0072] Furthermore, the thermal decomposition temperature of the isobutylene-based imidazole salt ionic polymer is 200 to 500°C.

[0073] Furthermore, the 5 wt % thermal weight loss temperature of the isobutylene-based imidazole salt ionic polymer is 220° C. or higher. Specific Embodiment IV

[0074] In one particular embodiment of the invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based pyridine salt ionic polymer, the polymer comprising structural unit A, structural unit B, and structural unit C; The structural unit A has a structure represented by formula (2-4) and / or formula (3-4) and, optionally, a structure represented by formula (1-4), the structural unit B has a structure represented by formula (4-4), and the structural unit C has a structure represented by formula (5-4). [ka] (wherein R1 is C1-C4 alkylene, R2 is C1-C4 alkyl, and R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a halogen atom, or C1 to C 20 Straight chain alkyl, C1-C 20 and X is Cl or Br. Furthermore, R1 is methylene or ethylene, R2 is methyl or ethyl, and R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, halogen, C1 to C 15 Straight chain alkyl, C1-C15 branched alkyl, nitro, amino, or cyano, and X is Br. Furthermore, R1 is methylene, R2 is methyl, and R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a halogen atom, or C1 to C 10 and X is a straight chain alkyl, amino, or cyano; and X is Br.

[0075] According to the present invention, based on the total molar amount of the polymer, the content of the structural unit A is 1 to 20 mol %, the content of the structural unit B is 0.5 to 10 mol %, and the content of the structural unit C is 75 to 97 mol %.

[0076] Furthermore, based on the total molar amount of the polymer, the content of the structural unit A is 2 to 15 mol %, the content of the structural unit B is 1 to 5 mol %, and the content of the structural unit C is 80 to 95 mol %.

[0077] According to the present invention, the content of pyridine salt functional groups is 1.5 to 35 mol % based on the total molar amount of the polymer.

[0078] Furthermore, the content of pyridine salt functional groups is 3 to 25 mol % based on the total molar amount of the polymer.

[0079] According to the present invention, based on the total molar amount of the polymer, the content of the side group benzylpyridine salt functional group is 1 to 20 mol %, and the content of the main chain tertiary carbon pyridine salt functional group is 0.5 to 15 mol %.

[0080] Furthermore, based on the total molar amount of the polymer, the content of side group benzylpyridine salt functional groups is 1.5 to 15 mol %, and the content of main chain tertiary carbon pyridine salt functional groups is 1 to 10 mol %.

[0081] According to the present invention, the thermal decomposition temperature of the isobutylene-based pyridine salt ionic polymer is 100 to 500°C.

[0082] According to the present invention, the 5 wt % thermal weight loss temperature of the isobutylene-based quaternary ammonium salt ionic polymer is 180° C. or higher.

[0083] Furthermore, the thermal decomposition temperature of the isobutylene-based pyridine salt ionic polymer is 150 to 450°C.

[0084] Furthermore, the 5 wt % thermal weight loss temperature of the isobutylene-based pyridine salt ionic polymer is 200° C. or higher.

[0085] In a second aspect of the present invention, there is provided a method for preparing an isobutylene-based cationic salt ionic polymer, said method comprising: Step (1) of dissolving a polymer in an organic solvent to obtain a polymer solution, and adding a halogen to the polymer solution to perform a halogenation reaction to obtain a halogenated polymer solution; and (2) adding at least one of a tertiary amine compound, a tertiary phosphine compound, an imidazole compound, and a pyridine compound to the halogenated polymer solution to carry out an ionization reaction, thereby obtaining the isobutylene-based cation salt ionic polymer; the polymer is a random copolymer of isobutylene and alkylstyrene; The halogenation reaction is carried out under irradiation with visible light, and the visible light is emitted in a pulsed manner.

[0086] In the present invention, the halogenation reaction of a random copolymer of isobutylene and alkylstyrene under irradiation with visible light, particularly pulsed visible light, not only increases the purity of the polymerization system, controls the rate of the halogenation reaction, and reduces the probability of halogenation side reactions, but more importantly, selectively controls the halogenation reaction to achieve a highly efficient and high degree of halogenation, thereby producing the isobutylene-based cationic salt ionic polymer described in the first aspect of the present invention. By containing cationic salt functional groups in both the side groups and the main chain of the polymer, the polymer has a high degree of polyionization and a high content of cationic salt functional groups. As an antibacterial agent, it can be used to prepare antibacterial polymeric materials such as antibacterial plastics, antibacterial rubber, antibacterial fibers, and antibacterial paints, and can effectively inhibit and kill bacteria, fungi, and pathogens.

[0087] In the present invention, a halogenation reaction of a polymer solution is carried out by the method of step (1), and the alkylstyrene-derived structural units of the polymer chain are subjected to a halogen substitution reaction, and both the alkyl hydrogen on the alkylstyrene benzene ring and the main chain tertiary carbon hydrogen connected to the benzene ring are halogenated, and further a side group alkyl halogen structure and a main chain tertiary carbon halogen structure can be formed in the polymer chain. Specifically, the alkylstyrene-derived structural units form the following three structures by halogenation: [ka]

[0088] Furthermore, in the present invention, the halogenation reaction is initiated by visible light in a specific wavelength range, which achieves the advantages of high controllability, fewer side reactions, and high selectivity. Specifically, the specific wavelength of visible light refers particularly to light waves in the yellow to red wavelength range, i.e., 560 to 630 nm, and is preferably an LED light source. In the present invention, the output power of the light source is 10 to 200 W.

[0089] In the present invention, the pulsed light emission means that the light source alternately emits and stops emitting light waves at equal time intervals. Specifically, the pulse duration of the pulsed light emission is 5 to 40 seconds, preferably 10 to 30 seconds.

[0090] In the present invention, the halogenation method by light irradiation of the present invention can achieve a halogenation reaction efficiency of 80% or more, preferably 90% or more.

[0091] In the present invention, the halogenation reaction efficiency means that, in a halogenation substitution reaction by a free radical mechanism, theoretically, when 100% of the halogen undergoes a hydrogen substitution reaction, 50% of the halogen is substituted by the polymer, and the ratio of the actually measured halogen content of the polymer to the theoretical halogen content is the halogenation reaction efficiency.

[0092] According to the present invention, the content of structural units provided by alkylstyrene is 3 to 25 mol %, and the content of structural units provided by isobutylene is 75 to 97 mol %, based on the total molar amount of the polymer.

[0093] Furthermore, based on the total molar amount of the polymer, the content of structural units derived from alkylstyrene is 5 to 20 mol %, and the content of structural units derived from isobutylene is 80 to 95 mol %.

[0094] According to the invention, the polymer has a weight average molecular weight M w is 1×10 4 ~1×10 5 and the molecular weight distribution coefficient is 2 to 3.5. Furthermore, the polymer has a weight average molecular weight M w is 2 x 10 4 ~8×10 4 and the molecular weight distribution coefficient is 2.2 to 3.

[0095] According to the invention, the content of aluminum ions in the polymer is less than 10 ppm, preferably less than 5 ppm.

[0096] In the present invention, the type of the organic solvent is not particularly limited, and may be an organic solvent commonly used in the relevant field, preferably a C6 to C8 10 Straight-chain alkanes, C6 to C 10 and at least one of a cycloalkane of C1 to C4, a halogenated alkane of C1 to C4, and the like, wherein the linear alkane includes at least one of n-hexane, n-heptane, n-octane, n-nonane, and n-decane, the cycloalkane includes cyclohexane, and the halogenated alkane includes at least one of dichloromethane, chloroform, and carbon tetrachloride.

[0097] According to the present invention, the molar ratio of the polymer to the halogen is 1:0.5-2, preferably 1:0.8-1.5, based on the molar content of the structural units provided by the alkylstyrene.

[0098] In the present invention, the halogen is preferably used after being diluted with a halogenated alkane, which is an organic solvent. The dilution concentration is not particularly limited as long as it allows easy control of the halogenation reaction.

[0099] In the present invention, the halogenation reaction is carried out in a light-shielded environment, and the temperature of the halogenation reaction is not particularly limited, and is, for example, carried out at room temperature.

[0100] According to the present invention, the halogenation reaction is preferably selectively controlled by mixing a halogen with an organic solvent to obtain a halogen solution, and then adding the halogen solution dropwise to the polymer solution to carry out the halogenation reaction.

[0101] In one preferred embodiment of the present invention, the dropping rate of the halogen solution is controlled so that the halogenation reaction time is 30 to 180 minutes.

[0102] In one specific embodiment of the present invention, a halogenated polymer solution is obtained by slowly adding a halogen solution dropwise to a polymer solution and carrying out a photohalogenation reaction under irradiation with pulsed visible light from an LED light source at 560 nm to 630 nm. To neutralize the hydrogen halide generated during the halogenation reaction, a certain amount of an alkaline compound such as sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, or magnesium oxide can be added to the polymer solution. The halogenated polymer solution is centrifuged or filtered to remove solid halide salt compounds, which are then used in the ionization reaction.

[0103] According to the present invention, the halogen is liquid bromine.

[0104] According to the present invention, the tertiary amine compound has a structure represented by formula (6). [ka] (However, R3, R4, and R5 are each independently C1 to C 20 Straight chain alkyl, C1-C 20 Branched alkyl, or C6-C 20 )

[0105] According to the present invention, the tertiary phosphine compound has a structure represented by formula (7). [ka] (However, R6, R7, and R8 are each independently C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl, or C6-C 10 )

[0106] According to the present invention, the imidazole compound has a structure represented by formula (8). [ka] (However, R9 is hydrogen, C1 to C 20 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, or C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6~C 10 and n is an integer of 0 to 5.

[0107] According to the present invention, the pyridine compound has a structure represented by formula (9). [ka] (However, R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a halogen atom, or C1 to C 20 Straight chain alkyl, C1-C 20 branched alkyl, nitro, amino, or cyano.

[0108] In one particular embodiment of the present invention, R3, R4, and R5 are each independently selected from the group consisting of C1 to C 18 or a C6 to C9 aryl, and preferably, R3, R4, and R5 are each independently methyl, C8 to C 16 or phenyl, and more preferably, R3 and R4 are methyl and R5 is C8 to C 16 or phenyl.

[0109] In one particular embodiment of the present invention, R6, R7, and R8 are each independently C1-C8 straight-chain alkyl, C5-C8 cycloalkyl, or C6-C8 aryl; preferably, R6, R7, and R8 are each independently C1-C8 straight-chain alkyl, cyclopentyl, cyclohexyl, or phenyl.

[0110] In one particular embodiment of the invention, R9 is hydrogen, C1-C 18 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, a C1-C5 linear alkyl, a C1-C5 branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6-C8 aryl, and n is an integer of 0 to 3. Preferably, R9 is hydrogen, C1-C 16 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, a C1 to C4 linear alkyl, hydroxy, nitro, cyano, amino, or phenyl.

[0111] In one particular embodiment of the present invention, R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, halogen, C1 to C 15 Straight chain alkyl, C1-C 15 branched alkyl, nitro, amino, or cyano, preferably R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, halogen, C1 to C 10 is a straight chain alkyl, amino, or cyano.

[0112] In the present invention, the tertiary amine compound represented by formula (6) is trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tris(undecyl)amine, tris(dodecyl)amine, tris(tridecyl)amine, tris(tetradecyl)amine, tris(pentadecyl)amine, tris(hexadecyl)amine, tris(heptadecyl)amine, tris(octadecyl)amine, tris(nonadecyl)amine, tris(eicosyl)amine, triphenylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, and N,N-dimethylbutylamine. , N,N-dimethylpentylamine, N,N-dimethylhexylamine, N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine, N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-dimethyleicosylamine, N,N-dimethylphenylamine, and the like are included, but are not limited thereto. Preferably, N,N-dimethylalkylamines, particularly N,N-dimethyl C8-C6 alkylamines, are used. 16 At least one of alkylamines, such as N,N-dimethyldecylamine, N,N-dimethyldodecylamine, and N,N-dimethyltetradecylamine, or a combination thereof.

[0113] In the present invention, the tertiary phosphine compound represented by formula (7) includes trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tripentylphosphine, tricyclopentylphosphine, trihexylphosphine, tricyclohexylphosphine, triheptylphosphine, trioctylphosphine, trinonylphosphine, tridecylphosphine, triphenylphosphine, dimethylphenylphosphine, dimethylethylphosphine, dimethylpropylphosphine, dimethylbutylphosphine, dimethylpentylphosphine, dimethylhexylphosphine, dimethylheptylphosphine, dimethyloctylphosphine, dimethylnonylphosphine, dimethyldecylphosphine, methylethylphenylphosphine, methylethylpropylphosphine, methylethylbutylphosphine, methylethylpentylphosphine, methylethylhexylphosphine, methylethylheptylphosphine, methylethyloctylphosphine, methylethylnonylphosphine, methylethyldecylphosphine, methylethylphenylphosphine, diethylphenylphosphine, Methyl phosphine, diethyl propyl phosphine, diethyl butyl phosphine, diethyl pentyl phosphine, diethyl hexyl phosphine, diethyl heptyl phosphine, diethyl octyl phosphine, diethyl nonyl phosphine, diethyl decyl phosphine, ethyl propyl phenyl phosphine, ethyl propyl butyl phosphine, ethyl propyl pentyl phosphine, ethyl propyl hexyl phosphine, ethyl propyl heptyl phosphine, ethyl propyl octyl phosphine, ethyl propyl nonyl phosphine, ethyl propyl decyl phosphine, dipropyl phenyl phosphine, dipropyl methyl phosphine, dipropyl ethyl phosphine, dipropyl butyl phosphine, dipropyl pentyl phosphine, dipropyl hexyl phosphine, dipropyl cyclohexyl phosphine, dipropyl heptyl phosphine, dipropyl octyl phosphine, dipropyl nonyl phosphine, dipropyl decyl phosphine, propyl butyl phenyl phosphine, propyl butyl pentyl phosphine, propyl butyl hexyl phosphine, propyl butyl heptyl phosphine, propyl butyl octyl phosphine,Propyl butyl nonyl phosphine, propyl butyl decyl phosphine, dibutyl phenyl phosphine, dibutyl methyl phosphine, dibutyl ethyl phosphine, dibutyl propyl phosphine, dibutyl pentyl phosphine, dibutyl hexyl phosphine, dibutyl cyclohexyl phosphine, dibutyl heptyl phosphine, dibutyl octyl phosphine, dibutyl nonyl phosphine, dibutyl decyl phosphine, dipentyl phenyl phosphine, dipentyl methyl phosphine, dipentyl ethyl phosphine, dipentyl propyl phosphine, dipentyl butyl dihexyl phosphine, dipentyl hexyl phosphine, dipentyl cyclohexyl phosphine, dipentyl heptyl phosphine, dipentyl octyl phosphine, dipentyl nonyl phosphine, dipentyl decyl phosphine, dihexyl phenyl phosphine, dihexyl methyl phosphine, dihexyl ethyl phosphine, dihexyl propyl phosphine, dihexyl butyl phosphine, dihexyl pentyl phosphine, dihexyl heptyl phosphine, dihexyl octyl phosphine, dihexyl nonyl phosphine, dihexyl decyl phosphine, dicyclohexyl dicyclohexylphenylphosphine, dicyclohexylmethylphosphine, dicyclohexylethylphosphine, dicyclohexylpropylphosphine, dicyclohexylbutylphosphine, dicyclohexylpentylphosphine, dicyclohexylheptylphosphine, dicyclohexyloctylphosphine, dicyclohexylnonylphosphine, dicyclohexyldecylphosphine, diheptylphenylphosphine, diheptylmethylphosphine, diheptylethylphosphine, diheptylpropylphosphine, diheptylbutylphosphine, diheptylpentylphosphine dioctyl phenyl phosphine, diheptyl hexyl phosphine, diheptyl octyl phosphine, diheptyl nonyl phosphine, diheptyl decyl phosphine, dioctyl phenyl phosphine, dioctyl methyl phosphine, dioctyl ethyl phosphine, dioctyl propyl phosphine, dioctyl butyl phosphine, dioctyl pentyl phosphine, dioctyl hexyl phosphine, dioctyl heptyl phosphine, dioctyl nonyl phosphine, dioctyl decyl phosphine, dinonyl phenyl phosphine, dinonyl methyl phosphine, dinonyl ethyl phosphine,The phosphine may include, but is not limited to, at least one of dinonylpropylphosphine, dinonylbutylphosphine, dinonylpentylphosphine, dinonylhexylphosphine, dinonylcyclohexylphosphine, dinonylheptylphosphine, dinonyloctylphosphine, dinonyldecylphosphine, didecylphenylphosphine, didecylmethylphosphine, didecylethylphosphine, didecylpropylphosphine, didecylbutylphosphine, didecylpentylphosphine, didecylhexylphosphine, didecylheptylphosphine, didecyloctylphosphine, and didecylnonylphosphine. In the present invention, preferred phosphine compounds are tricyclohexylphosphine and triphenylphosphine.

[0114] In the present invention, the imidazole compound represented by formula (8) is imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1-octylimidazole, 1-nonylimidazole, 1-decylimidazole, 1-undecylimidazole, 1-dodecylimidazole. 1-Tridecylimidazole, 1-tetradecylimidazole, 1-pentadecylimidazole, 1-hexadecylimidazole, 1-heptadecylimidazole, 1-octadecylimidazole, 1,2-dimethylimidazole, 1,2-diethylimidazole, 1,2-dipropylimidazole, 1,2-dibutylimidazole, 1-methyl-2-ethylimidazole, 1-methyl-2-propylimidazoline 1-methyl-2-butylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-pentylimidazole, 2-hexylimidazole, 2-heptylimidazole, 2-octylimidazole, 2-nonylimidazole, 2-decylimidazole, 2-nitroimidazole, 4-nitroimidazole, 5-nitroimidazole, 1-methyl 1-methyl-5-nitroimidazole, 1-ethyl-4-nitroimidazole, 1-ethyl-5-nitroimidazole, 1-propyl-4-nitroimidazole, 1-propyl-5-nitroimidazole, 1-butyl-4-nitroimidazole, 1-butyl-5-nitroimidazole, 2-methyl-5-nitroimidazole, 1-butyl-2-methyl-4-nitroimidazole, 1,The alkylimidazoles include, but are not limited to, at least one of 2-dimethyl-5-nitroimidazole, 2-chloro-4-nitroimidazole, 2-chloro-5-nitroimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, tolueneimidazole, benzimidazole, and 2-aminobenzimidazole. In the present invention, the alkylimidazoles are preferably 1-alkylimidazoles (N-alkylimidazoles).

[0115] In the present invention, the pyridine compound represented by formula (9) is pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 5-methylpyridine, 6-methylpyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 5-ethylpyridine, 6-ethylpyridine, 2,6-diethylpyridine, 2,4,6-triethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, 5-propylpyridine, pyridine, 6-propylpyridine, 2,6-dipropylpyridine, 2,4,6-tripropylpyridine, 2-butylpyridine, 3-butylpyridine, 4-butylpyridine, 5-butylpyridine, 6-butylpyridine, 2,6-dibutylpyridine, 2,4,6-tributylpyridine, 2-pentylpyridine, 3-pentylpyridine, 4-pentylpyridine, 5-pentylpyridine, 6-pentylpyridine, 2,6-dipentylpyridine, 2,4,6-tripentylpyridine, 2-hexylpyridine, 3-hexylpyridine, Xylpyridine, 4-hexylpyridine, 5-hexylpyridine, 6-hexylpyridine, 2-heptylpyridine, 3-heptylpyridine, 4-heptylpyridine, 5-heptylpyridine, 6-heptylpyridine, 2-octylpyridine, 3-octylpyridine, 4-octylpyridine, 5-octylpyridine, 6-octylpyridine, 2-nonylpyridine, 3-nonylpyridine, 4-nonylpyridine, 5-nonylpyridine, 6-nonylpyridine, 2-decylpyridine, 3-decylpyridine, 4-decylpyridine Lysine, 5-decylpyridine, 6-decylpyridine, 4-undecylpyridine, 4-dodecylpyridine, 4-tridecylpyridine, 4-tetradecylpyridine, 4-pentadecylpyridine, 4-hexadecylpyridine, 4-heptadecylpyridine, 4-octadecylpyridine, 4-nonadecylpyridine, 4-eicosylpyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 5-hydroxypyridine, 6-hydroxypyridine, 2,6-dihydroxypyridine, 2,4,The alkylpyridine may include, but is not limited to, at least one of 6-trihydroxypyridine, 2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine, 5-fluoropyridine, 6-fluoropyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 5-chloropyridine, 6-chloropyridine, 2,3-dichloropyridine, 2,3,6-trichloropyridine, 2,6-diamino-3,5-dinitropyridine, 2,6-diaminopyridine, 2,4,6-triaminopyridine, 2,4,6-trinitropyridine, 2,4,6-trichloropyridine, and 2,4,6-tribromopyridine, and is preferably a 4-alkylpyridine in the present invention.

[0116] In one specific embodiment of the present invention, a compound containing at least one of a tertiary amine compound, a tertiary phosphine compound, an imidazole compound, and a pyridine compound is dissolved in a halogenated alkane in an organic solvent, and the solution is added to a halogenated polymer solution, followed by an ionization reaction in the presence of a protective gas. The reaction temperature is 20 to 150°C, preferably 40 to 120°C, and the reaction time is 1 to 24 hours, preferably 2 to 20 hours.

[0117] According to the present invention, the molar ratio of at least one of the tertiary amine compound, tertiary phosphine compound, imidazole compound and pyridine compound to the halogen is 0.8 to 1.5:1, preferably 0.9 to 1.2:1.

[0118] In the present invention, when the ionization reaction has progressed to a certain extent, the solid insoluble matter is precipitated from the organic solvent, and after the reaction is completed, the solvent is separated by filtration, and the insoluble ionic polymer is washed with hexane once or twice and then vacuum dried to obtain the isobutylene-based cation salt ionic polymer according to the first aspect of the present invention. Specific Embodiment I

[0119] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary ammonium salt ionic polymer, and the method for preparing the isobutylene-based quaternary ammonium salt ionic polymer comprises: Step (1) of dissolving a polymer in an organic solvent to obtain a polymer solution, and adding a halogen to the polymer solution to perform a halogenation reaction to obtain a halogenated polymer solution; Step (2) adding a tertiary amine to the halogenated polymer solution to carry out an ionization reaction to obtain the isobutylene-based quaternary ammonium salt ionic polymer; the polymer is a random copolymer of isobutylene and alkylstyrene; The halogenation reaction is carried out under irradiation with visible light, and the visible light mode is pulsed emission.

[0120] Furthermore, in the present invention, the halogenation reaction is initiated by visible light of a specific wavelength range, which achieves the advantages of high controllability, fewer side reactions, and high selectivity. Specifically, the specific wavelength of visible light refers particularly to light waves in the yellow to red wavelength range, i.e., 560 to 630 nm, and is preferably an LED light source. In the present invention, the output power of the light source is 10 to 200 W.

[0121] In the present invention, the pulsed light emission means that the light source alternately emits and stops emitting light waves at equal time intervals. Specifically, the pulse duration of the pulsed light emission is 5 to 40 seconds, preferably 10 to 30 seconds.

[0122] In the present invention, the halogenation method by light irradiation of the present invention can achieve a halogenation reaction efficiency of 80% or more, preferably 90% or more.

[0123] In the present invention, the halogenation reaction efficiency means that, in a halogenation substitution reaction by a free radical mechanism, theoretically, when 100% of the halogen undergoes a hydrogen substitution reaction, 50% of the halogen is substituted by the polymer, and the ratio of the actually measured halogen content of the polymer to the theoretical halogen content is the halogenation reaction efficiency.

[0124] According to the present invention, the content of structural units provided by alkylstyrene is 3 to 25 mol %, and the content of structural units provided by isobutylene is 75 to 97 mol %, based on the total molar amount of the polymer.

[0125] Furthermore, based on the total molar amount of the polymer, the content of structural units derived from alkylstyrene is 5 to 20 mol %, and the content of structural units derived from isobutylene is 80 to 95 mol %.

[0126] According to the invention, the polymer has a weight average molecular weight M w is 1×10 4 ~1×10 5 and the molecular weight distribution coefficient is 2 to 3.5. Furthermore, the polymer has a weight average molecular weight M w is 2 x 10 4 ~8×10 4 and the molecular weight distribution coefficient is 2.2 to 3.

[0127] According to the invention, the content of aluminum ions in the polymer is less than 10 ppm, preferably less than 5 ppm.

[0128] In the present invention, the type of the organic solvent is not particularly limited, and may be an organic solvent commonly used in the relevant field, preferably a C6 to C8 10 Straight-chain alkanes, C6 to C 10and at least one of a cycloalkane of C1 to C4, a C1 to C4 halogenated alkane, and the like, wherein the linear alkane includes at least one of n-hexane, n-heptane, n-octane, n-nonane, and n-decane, the cycloalkane includes cyclohexane, and the halogenated alkane includes at least one of dichloromethane, chloroform, and carbon tetrachloride.

[0129] According to the present invention, the molar ratio of the polymer to the halogen is 1:0.5-2, preferably 1:0.8-1.5, based on the molar content of the structural units provided by the alkylstyrene.

[0130] In the present invention, the halogen is preferably used after being diluted with a halogenated alkane, which is an organic solvent. The dilution concentration is not particularly limited as long as it allows easy control of the halogenation reaction.

[0131] In the present invention, the halogenation reaction is carried out in a light-shielded environment, and the temperature of the halogenation reaction is not particularly limited, and is, for example, carried out at room temperature.

[0132] According to the present invention, the halogenation reaction is preferably selectively controlled by mixing a halogen with an organic solvent to obtain a halogen solution, and then adding the halogen solution dropwise to the polymer solution to carry out the halogenation reaction.

[0133] In one preferred embodiment of the present invention, the dropping rate of the halogen solution is controlled so that the halogenation reaction time is 30 to 180 minutes.

[0134] In one specific embodiment of the present invention, a halogenated polymer solution is obtained by slowly adding a halogen solution dropwise to a polymer solution and carrying out a photohalogenation reaction under irradiation with pulsed visible light from an LED light source at 560 nm to 630 nm. To neutralize the hydrogen halide generated during the halogenation reaction, a certain amount of an alkaline compound such as sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, or magnesium oxide can be added to the polymer solution. The halogenated polymer solution is centrifuged or filtered to remove solid halide salt compounds, which are then used in the ionization reaction.

[0135] According to the present invention, the halogen is liquid bromine.

[0136] According to the present invention, the tertiary amine has a structure represented by formula (6). [ka] (However, R3, R4, and R5 are each independently C1 to C 20 Straight chain alkyl, C1-C 20 Branched alkyl, or C6-C 20 is an aryl of Furthermore, R3, R4, and R5 are each independently selected from C1 to C 18 and C6 to C9 aryl. Furthermore, R3 and R4 are methyl, and R5 is C8 to C 16 It is a straight chain alkyl or phenyl.

[0137] In the present invention, the tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tris(undecyl)amine, tris(dodecyl)amine, tris(tridecyl)amine, tris(tetradecyl)amine, tris(pentadecyl)amine, tris(hexadecyl)amine, tris(heptadecyl)amine, tris(octadecyl)amine, tris(nonadecyl)amine, tris(eicosyl)amine, triphenylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, and N,N-dimethylethylamine. Tertiary amines include, but are not limited to, dimethylpentylamine, N,N-dimethylhexylamine, N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine, N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-dimethyleicosylamine, N,N-dimethylphenylamine, and the like. Preferably, the tertiary amine is an N,N-dimethylalkylamine, particularly an N,N-dimethyl C8-C6 alkylamine. 16 At least one of alkylamines, such as N,N-dimethyldecylamine, N,N-dimethyldodecylamine, and N,N-dimethyltetradecylamine, or a combination thereof.

[0138] In one specific embodiment of the present invention, a tertiary amine is dissolved in a halogenated alkane, which is an organic solvent, and the solution is added to a halogenated polymer solution to carry out an ionization reaction in the presence of a protective gas. The reaction temperature is 20 to 100°C, preferably 40 to 80°C, and the reaction time is 1 to 10 hours, preferably 2 to 8 hours.

[0139] According to the present invention, the molar ratio of the tertiary amine to the halogen is 0.8 to 1.5:1, preferably 0.9 to 1.2:1.

[0140] In the present invention, when the ionization reaction has progressed to a certain extent, the solid insoluble matter is precipitated from the organic solvent, and after the reaction is completed, the solvent is separated by filtration, and the insoluble ionic polymer is washed with hexane once or twice and then dried in a vacuum to obtain the isobutylene-based quaternary ammonium salt ionic polymer. Specific Embodiment II

[0141] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary phosphonium salt ionic polymer, and the method for preparing the isobutylene-based quaternary phosphonium salt ionic polymer comprises: Step (1) of dissolving a polymer in an organic solvent to obtain a polymer solution, and adding a halogen to the polymer solution to perform a halogenation reaction to obtain a halogenated polymer solution; and (2) adding a tertiary phosphine to the halogenated polymer solution to carry out an ionization reaction to obtain the isobutylene-based quaternary phosphonium salt ionic polymer; The polymer is a random copolymer of isobutylene and alkylstyrene, the halogenation reaction is carried out under irradiation with visible light, and the visible light mode is pulsed emission.

[0142] Furthermore, in the present invention, the halogenation reaction is initiated by visible light of a specific wavelength range, which achieves the advantages of high controllability, fewer side reactions, and high selectivity. Specifically, the specific wavelength of visible light refers particularly to light waves in the yellow to red wavelength range, i.e., 560 to 630 nm, and is preferably an LED light source. In the present invention, the output power of the light source is 10 to 200 W.

[0143] In the present invention, the pulsed light emission means that the light source alternately emits and stops emitting light waves at equal time intervals. Specifically, the pulse duration of the pulsed light emission is 5 to 40 seconds, preferably 10 to 30 seconds.

[0144] In the present invention, the halogenation method by light irradiation of the present invention can achieve a halogenation reaction efficiency of 80% or more, preferably 90% or more.

[0145] In the present invention, the halogenation reaction efficiency means that, in a halogenation substitution reaction by a free radical mechanism, theoretically, when 100% of the halogen undergoes a hydrogen substitution reaction, 50% of the halogen is substituted by the polymer, and the ratio of the actually measured halogen content of the polymer to the theoretical halogen content is the halogenation reaction efficiency.

[0146] According to the present invention, the molar ratio of the polymer to the halogen is 1:0.5-2, preferably 1:0.8-1.5, based on the molar content of the structural units provided by the alkylstyrene.

[0147] According to the present invention, the halogen is liquid bromine.

[0148] In the present invention, the halogenation reaction is carried out in a light-shielded environment, and the temperature of the halogenation reaction is not particularly limited, and is, for example, carried out at room temperature.

[0149] According to the present invention, the halogenation reaction is preferably selectively controlled by mixing a halogen with an organic solvent to obtain a halogen solution, and then adding the halogen solution dropwise to the polymer solution to carry out the halogenation reaction.

[0150] In the present invention, the concentration of the halogen solution is not particularly limited as long as the halogenation reaction can be easily controlled. In one preferred embodiment of the present invention, the dropping rate of the halogen solution is controlled so that the halogenation reaction time is 30 to 180 minutes.

[0151] In one specific embodiment of the present invention, a halogenated polymer solution is obtained by slowly adding a halogen solution dropwise to a polymer solution and carrying out a photohalogenation reaction under irradiation with pulsed visible light. To neutralize the hydrogen halide generated during the halogenation reaction, a certain amount of an alkaline compound such as sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, or magnesium oxide can be added to the polymer solution. The halogenated polymer solution is centrifuged or filtered to remove solid halide salt compounds, which are then used in the ionization reaction.

[0152] According to the present invention, the content of structural units provided by alkylstyrene is 3 to 25 mol %, and the content of structural units provided by isobutylene is 75 to 97 mol %, based on the total molar amount of the polymer.

[0153] Furthermore, based on the total molar amount of the polymer, the content of structural units derived from alkylstyrene is 5 to 20 mol %, and the content of structural units derived from isobutylene is 80 to 95 wt %.

[0154] According to the invention, the polymer has a weight average molecular weight M w is 1×10 4 ~1×10 5 and the molecular weight distribution coefficient is 2 to 3.5. Furthermore, the polymer has a weight average molecular weight M w is 2 x 10 4 ~8×10 4 and the molecular weight distribution coefficient is 2.2 to 3.

[0155] According to the invention, the content of aluminum ions in the polymer is less than 10 ppm, preferably less than 5 ppm.

[0156] In the present invention, the type of the organic solvent is not particularly limited, and may be an organic solvent commonly used in the relevant field, preferably a C6 to C8 10 Straight-chain alkanes, C6 to C10 and at least one of a cycloalkane of C1 to C4, a C1 to C4 halogenated alkane, and the like, wherein the linear alkane includes at least one of n-hexane, n-heptane, n-octane, n-nonane, and n-decane, the cycloalkane includes cyclohexane, and the halogenated alkane includes at least one of dichloromethane, chloroform, and carbon tetrachloride.

[0157] According to the present invention, the tertiary phosphine has a structure shown in formula (7). [ka] (However, R6, R7, and R8 are each independently C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl, or C6-C 10 is an aryl of Furthermore, R6, R7, and R8 are each independently C1 to C8 linear alkyl, C5 to C8 cycloalkyl, or C6 to C8 aryl. Furthermore, R6, R7, and R8 are each independently a C1 to C8 linear alkyl, cyclopentyl, cyclohexyl, or phenyl.

[0158] In the present invention, the tertiary phosphine may be trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tripentylphosphine, tricyclopentylphosphine, trihexylphosphine, tricyclohexylphosphine, triheptylphosphine, trioctylphosphine, trinonylphosphine, tridecylphosphine, triphenylphosphine, dimethylphenylphosphine, dimethylethylphosphine, dimethylpropylphosphine, dimethylbutylphosphine, dimethylpentylphosphine, dimethylhexylphosphine, dimethylheptylphosphine, dimethyloctylphosphine, dimethylnonylphosphine, dimethyldecylphosphine, methylethylphenylphosphine, methylethylpropylphosphine, methylethylbutylphosphine, methylethylpentylphosphine, methylethylhexylphosphine, methylethylheptylphosphine, methylethyloctylphosphine, methylethylnonylphosphine, methylethyldecylphosphine, methylethylphenylphosphine, diethylphenylphosphine, diethylmethylphosphine, phosphine, diethyl propyl phosphine, diethyl butyl phosphine, diethyl pentyl phosphine, diethyl hexyl phosphine, diethyl heptyl phosphine, diethyl octyl phosphine, diethyl nonyl phosphine, diethyl decyl phosphine, ethyl propyl phenyl phosphine, ethyl propyl butyl phosphine, ethyl propyl pentyl phosphine, ethyl propyl hexyl phosphine, ethyl propyl heptyl phosphine, ethyl propyl octyl phosphine, ethyl propyl nonyl phosphine, ethyl propyl decyl phosphine, dipropyl phenyl phosphine, dipropyl methyl phosphine, dipropyl ethyl phosphine, dipropyl butyl phosphine, dipropyl pentyl phosphine, dipropyl hexyl phosphine, dipropyl cyclohexyl phosphine, dipropyl heptyl phosphine, dipropyl octyl phosphine, dipropyl nonyl phosphine, dipropyl decyl phosphine, propyl butyl phenyl phosphine, propyl butyl pentyl phosphine, propyl butyl hexyl phosphine, propyl butyl heptyl phosphine, propyl butyl octyl phosphine,Propyl butyl nonyl phosphine, propyl butyl decyl phosphine, dibutyl phenyl phosphine, dibutyl methyl phosphine, dibutyl ethyl phosphine, dibutyl propyl phosphine, dibutyl pentyl phosphine, dibutyl hexyl phosphine, dibutyl cyclohexyl phosphine, dibutyl heptyl phosphine, dibutyl octyl phosphine, dibutyl nonyl phosphine, dibutyl decyl phosphine, dipentyl phenyl phosphine, dipentyl methyl phosphine, dipentyl ethyl phosphine, dipentyl propyl phosphine, dipentyl butyl dihexyl phosphine, dipentyl hexyl phosphine, dipentyl cyclohexyl phosphine, dipentyl heptyl phosphine, dipentyl octyl phosphine, dipentyl nonyl phosphine, dipentyl decyl phosphine, dihexyl phenyl phosphine, dihexyl methyl phosphine, dihexyl ethyl phosphine, dihexyl propyl phosphine, dihexyl butyl phosphine, dihexyl pentyl phosphine, dihexyl heptyl phosphine, dihexyl octyl phosphine, dihexyl nonyl phosphine, dihexyl decyl phosphine, dicyclohexyl dicyclohexylphenylphosphine, dicyclohexylmethylphosphine, dicyclohexylethylphosphine, dicyclohexylpropylphosphine, dicyclohexylbutylphosphine, dicyclohexylpentylphosphine, dicyclohexylheptylphosphine, dicyclohexyloctylphosphine, dicyclohexylnonylphosphine, dicyclohexyldecylphosphine, diheptylphenylphosphine, diheptylmethylphosphine, diheptylethylphosphine, diheptylpropylphosphine, diheptylbutylphosphine, diheptylpentylphosphine dioctyl phenyl phosphine, diheptyl hexyl phosphine, diheptyl octyl phosphine, diheptyl nonyl phosphine, diheptyl decyl phosphine, dioctyl phenyl phosphine, dioctyl methyl phosphine, dioctyl ethyl phosphine, dioctyl propyl phosphine, dioctyl butyl phosphine, dioctyl pentyl phosphine, dioctyl hexyl phosphine, dioctyl heptyl phosphine, dioctyl nonyl phosphine, dioctyl decyl phosphine, dinonyl phenyl phosphine, dinonyl methyl phosphine, dinonyl ethyl phosphine,The phosphine may include, but is not limited to, at least one of dinonylpropylphosphine, dinonylbutylphosphine, dinonylpentylphosphine, dinonylhexylphosphine, dinonylcyclohexylphosphine, dinonylheptylphosphine, dinonyloctylphosphine, dinonyldecylphosphine, didecylphenylphosphine, didecylmethylphosphine, didecylethylphosphine, didecylpropylphosphine, didecylbutylphosphine, didecylpentylphosphine, didecylhexylphosphine, didecylheptylphosphine, didecyloctylphosphine, and didecylnonylphosphine. In the present invention, preferred phosphine compounds are tricyclohexylphosphine and triphenylphosphine.

[0159] In one specific embodiment of the present invention, a tertiary phosphine is dissolved in a halogenated alkane, which is an organic solvent, and the solution is added to a halogenated polymer solution to carry out an ionization reaction in the presence of a protective gas, the reaction temperature being 60 to 150°C, preferably 80 to 120°C, and the reaction time being 4 to 24 hours, preferably 6 to 20 hours.

[0160] According to the present invention, the molar ratio of the tertiary phosphine to the halogen is 0.8-1.5:1, preferably 0.9-1.2:1.

[0161] In the present invention, when the ionization reaction has progressed to a certain extent, the solid insoluble matter is precipitated from the organic solvent, and after the reaction is completed, the solvent is separated by filtration, and the insoluble ionic salt polymer is washed with hexane once or twice and then vacuum dried to obtain the isobutylene-based quaternary phosphonium salt ionic polymer. Specific Embodiment III

[0162] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based imidazole salt ionic polymer, and the method for preparing the isobutylene-based imidazole salt ionic polymer comprises: Step (1) of dissolving a polymer in an organic solvent to obtain a polymer solution, and adding a halogen to the polymer solution to perform a halogenation reaction to obtain a halogenated polymer solution; (2) adding imidazole to the halogenated polymer solution to carry out an ionization reaction to obtain the isobutylene-based imidazole salt ionic polymer; The polymer is a random copolymer of isobutylene and alkylstyrene, the halogenation reaction is carried out under irradiation with visible light, and the visible light mode is pulsed emission.

[0163] Furthermore, in the present invention, the halogenation reaction is initiated by visible light of a specific wavelength range, which achieves the advantages of high controllability, fewer side reactions, and high selectivity. Specifically, the specific wavelength of visible light refers particularly to light waves in the yellow to red wavelength range, i.e., 560 to 630 nm, and is preferably an LED light source. In the present invention, the output power of the light source is 10 to 200 W.

[0164] In the present invention, the pulsed light emission means that the light source alternately emits and stops emitting light waves at equal time intervals. Specifically, the pulse duration of the pulsed light emission is 5 to 40 seconds, preferably 10 to 30 seconds.

[0165] According to the present invention, the molar ratio of the polymer to the halogen is 1:0.5-2, preferably 1:0.8-1.5, based on the molar content of the structural units provided by the alkylstyrene.

[0166] In the present invention, by controlling the molar ratio of halogen to polymer so as to satisfy the above range under irradiation with visible light, the halogenation reaction efficiency can be increased to 80% or more, preferably 90% or more.

[0167] In the present invention, the halogenation reaction efficiency means that, in a halogenation substitution reaction by a free radical mechanism, theoretically, when 100% of the halogen undergoes a hydrogen substitution reaction, 50% of the halogen is substituted by the polymer, and the ratio of the actually measured halogen content of the polymer to the theoretical halogen content is the halogenation reaction efficiency.

[0168] In the present invention, the halogen is preferably diluted with an organic solvent before use, and the dilution concentration is not particularly limited as long as it allows easy control of the halogenation reaction. The type of organic solvent is not particularly limited, and may be an organic solvent commonly used in the field, such as a halogenated alkane and / or alkane.

[0169] In the present invention, the halogenation reaction is carried out in a light-shielded environment, and the temperature of the halogenation reaction is not particularly limited, and is, for example, carried out at room temperature.

[0170] According to the present invention, the halogenation reaction is preferably controlled selectively by mixing a halogen with an organic solvent to obtain a halogen solution, and then adding the halogen solution dropwise to the polymer solution to carry out the halogenation reaction.

[0171] In one preferred embodiment of the present invention, the dropping rate of the halogen solution is controlled so that the halogenation reaction time is 30 to 180 minutes.

[0172] In one specific embodiment of the present invention, a halogen solution is slowly added dropwise to a polymer solution, and a photohalogenation reaction is carried out under irradiation with pulsed visible light to obtain a halogenated polymer solution. A certain amount of an alkaline compound such as sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, or magnesium oxide can be added to the polymer solution to neutralize the hydrogen halide generated during the halogenation reaction.

[0173] The halogenated polymer solution is centrifuged or filtered to remove solid halide salt compounds for use in the ionization reaction.

[0174] According to the present invention, the halogen is liquid bromine.

[0175] According to the present invention, the content of structural units provided by alkylstyrene is 3 to 25 mol %, and the content of structural units provided by isobutylene is 75 to 97 mol %, based on the total molar amount of the polymer.

[0176] Furthermore, based on the total molar amount of the polymer, the content of structural units derived from alkylstyrene is 5 to 20 mol %, and the content of structural units derived from isobutylene is 80 to 95 wt %.

[0177] According to the invention, the polymer has a weight average molecular weight M w is 1×10 4 ~1×10 5 and the molecular weight distribution coefficient is 2 to 3.5. Furthermore, the polymer has a weight average molecular weight M w is 2 x 10 4 ~8×10 4 and the molecular weight distribution coefficient is 2.2 to 3.

[0178] According to the invention, the content of aluminum ions in the polymer is less than 10 ppm, preferably less than 5 ppm.

[0179] In the present invention, the type of the organic solvent is not particularly limited, and may be an organic solvent commonly used in the relevant field, preferably a C6 to C8 10 Straight-chain alkanes, C6 to C 10 and at least one of a cycloalkane of C1 to C4, a C1 to C4 halogenated alkane, and the like, wherein the linear alkane includes at least one of n-hexane, n-heptane, n-octane, n-nonane, and n-decane, the cycloalkane includes cyclohexane, and the halogenated alkane includes at least one of dichloromethane, chloroform, and carbon tetrachloride.

[0180] According to the present invention, the imidazole has a structure represented by formula (8). [ka] (However, R9 is hydrogen, C1 to C 20 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, or C1 to C 10 Straight chain alkyl, C1-C 10 Branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6~C 10 and n is an integer of 0 to 5. Furthermore, R9 is hydrogen, C1 to C 18 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, a C1-C5 linear alkyl, a C1-C5 branched alkyl, hydroxy, nitro, -(CH2) n -NH2, cyano, or C6-C8 aryl, and n is an integer of 0-3. Furthermore, R9 is hydrogen, C1 to C 16 is a linear alkyl group of R 10 , R 11 , R 12 are each independently hydrogen, a halogen atom, a C1-C4 linear alkyl, hydroxy, nitro, cyano, amino, or phenyl.

[0181] In the present invention, the imidazole compound is imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1-octylimidazole, 1-nonylimidazole, 1-decylimidazole, 1-undecylimidazole, 1-dodecylimidazole, 1-tridecylimidazole, 1-tetradecylimidazole, 1-pentadecylimidazole, 1-hexadecylimidazole, 1-heptadecylimidazole, azole, 1-octadecylimidazole, 1,2-dimethylimidazole, 1,2-diethylimidazole, 1,2-dipropylimidazole, 1,2-dibutylimidazole, 1-methyl-2-ethylimidazole, 1-methyl-2-propylimidazole, 1-methyl-2-butylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-pentylimidazole, 2-hexylimidazole, 2-heptylimidazole, 2-octylimidazole, 2-nonylimidazole, 2- Decylimidazole, 2-nitroimidazole, 4-nitroimidazole, 5-nitroimidazole, 1-methyl-4-nitroimidazole, 1-methyl-5-nitroimidazole, 1-ethyl-4-nitroimidazole, 1-ethyl-5-nitroimidazole, 1-propyl-4-nitroimidazole, 1-propyl-5-nitroimidazole, 1-butyl-4-nitroimidazole, 1-butyl-5-nitroimidazole, 2-methyl-5-nitroimidazole, 1-butyl-2-methyl-4-nitroimidazole, 1,2-dimethyl-5-nitroimidazole The alkylimidazoles include, but are not limited to, at least one of 1-methylimidazole, 2-chloro-4-nitroimidazole, 2-chloro-5-nitroimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, tolueneimidazole, benzimidazole, and 2-aminobenzimidazole, and in the present invention, preferred is 1-alkylimidazole (N-alkylimidazole).

[0182] In one specific embodiment of the present invention, an imidazole compound is dissolved in a halogenated alkane, which is an organic solvent, and the solution is added to a halogenated polymer solution to carry out an ionization reaction in the presence of a protective gas. The reaction temperature is 60 to 120°C, preferably 70 to 100°C, and the reaction time is 6 to 20 hours, preferably 8 to 16 hours.

[0183] According to the present invention, the molar ratio of the imidazole to the halogen is 0.8 to 1.5:1, preferably 0.9 to 1.2:1.

[0184] In the present invention, when the ionization reaction has progressed to a certain extent, the solid insoluble matter is precipitated from the organic solvent, and after the reaction is completed, the solvent is separated, and the insoluble ionic polymer is washed with hexane once or twice and then vacuum dried to obtain the isobutylene-based imidazole salt ionic polymer. Specific Embodiment IV

[0185] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based pyridine salt ionic polymer, and the method for preparing the isobutylene-based pyridine salt ionic polymer comprises: Step (1) of dissolving a polymer in an organic solvent to obtain a polymer solution, and adding a halogen to the polymer solution to perform a halogenation reaction to obtain a halogenated polymer solution; (2) adding pyridine to the halogenated polymer solution to carry out an ionization reaction to obtain the isobutylene-based pyridine salt ionic polymer; the polymer is a random copolymer of isobutylene and alkylstyrene; The halogenation reaction is carried out under irradiation with visible light, and the visible light mode is pulsed emission.

[0186] Furthermore, in the present invention, the halogenation reaction is initiated by visible light of a specific wavelength range, which achieves the advantages of high controllability, fewer side reactions, and high selectivity. Specifically, the specific wavelength of visible light refers particularly to light waves in the yellow to red wavelength range, i.e., 560 to 630 nm, and is preferably an LED light source. In the present invention, the output power of the light source is 10 to 200 W.

[0187] In the present invention, the pulsed light emission means that the light source alternately emits and stops emitting light waves at equal time intervals. Specifically, the pulse duration of the pulsed light emission is 5 to 40 seconds, preferably 10 to 30 seconds.

[0188] In the present invention, the halogenation method by light irradiation of the present invention can achieve a halogenation reaction efficiency of 80% or more, preferably 90% or more.

[0189] In the present invention, the halogenation reaction efficiency means that, in a halogenation substitution reaction by a free radical mechanism, theoretically, when 100% of the halogen undergoes a hydrogen substitution reaction, 50% of the halogen is substituted by the polymer, and the ratio of the actually measured halogen content of the polymer to the theoretical halogen content is the halogenation reaction efficiency.

[0190] According to the present invention, the molar ratio of the polymer to the halogen is 1:0.5-2, preferably 1:0.8-1.5, based on the molar content of the structural unit provided by the alkylstyrene.

[0191] According to the present invention, the halogen is liquid bromine.

[0192] In the present invention, the halogenation reaction is carried out in a light-shielded environment, and the temperature of the halogenation reaction is not particularly limited, and is, for example, carried out at room temperature.

[0193] In the present invention, the halogen is preferably used after being diluted with an organic solvent, and the dilution concentration is not particularly limited as long as it allows easy control of the halogenation reaction.

[0194] According to the present invention, the halogenation reaction is preferably selectively controlled by mixing a halogen with an organic solvent to obtain a halogen solution, and then adding the halogen solution dropwise to the polymer solution to carry out the halogenation reaction.

[0195] In the present invention, the concentration of the halogen solution is not particularly limited as long as the halogenation reaction can be easily controlled.

[0196] In one preferred embodiment of the present invention, the dropping rate of the halogen solution is controlled so that the halogenation reaction time is 30 to 180 minutes.

[0197] In one specific embodiment of the present invention, a halogenated polymer solution is obtained by slowly adding a halogen solution dropwise to a polymer solution and carrying out a photohalogenation reaction under irradiation with pulsed visible light. To neutralize the hydrogen halide generated during the halogenation reaction, a certain amount of an alkaline compound such as sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, or magnesium oxide can be added to the polymer solution. The halogenated polymer solution is centrifuged or filtered to remove solid halide salt compounds, which are then used in the ionization reaction.

[0198] According to the present invention, the content of structural units provided by alkylstyrene is 3 to 25 mol %, and the content of structural units provided by isobutylene is 75 to 97 mol %, based on the total molar amount of the polymer.

[0199] Furthermore, based on the total molar amount of the polymer, the content of structural units derived from alkylstyrene is 5 to 20 mol %, and the content of structural units derived from isobutylene is 80 to 95 mol %.

[0200] According to the invention, the polymer has a weight average molecular weight M w is 1×10 4 ~1×10 5 and the molecular weight distribution coefficient is 2 to 3.5. Furthermore, the polymer has a weight average molecular weight M w is 2 x 10 4 ~8×10 4 and the molecular weight distribution coefficient is 2.2 to 3.

[0201] According to the invention, the content of aluminum ions in the polymer is less than 10 ppm, preferably less than 5 ppm.

[0202] In the present invention, the type of the organic solvent is not particularly limited, and may be an organic solvent commonly used in the relevant field, preferably a C6 to C8 10 Straight-chain alkanes, C6 to C 10 and at least one of a cycloalkane of C1 to C4, a C1 to C4 halogenated alkane, and the like, wherein the linear alkane includes at least one of n-hexane, n-heptane, n-octane, n-nonane, and n-decane, the cycloalkane includes cyclohexane, and the halogenated alkane includes at least one of dichloromethane, chloroform, and carbon tetrachloride.

[0203] According to the present invention, the pyridine has a structure represented by formula (9). [ka] (However, R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a halogen atom, or C1 to C 20 Straight chain alkyl, C1-C 20 branched alkyl, nitro, amino, or cyano. Furthermore, R 13 , R 14 , R 15 , R16 , R 17 are each independently hydrogen, halogen, C1 to C 15 Straight chain alkyl, C1-C 15 branched alkyl, nitro, amino, or cyano. Furthermore, R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, halogen, C1 to C 10 ) is a straight chain alkyl, amino, or cyano.

[0204] In the present invention, the pyridine is pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 5-methylpyridine, 6-methylpyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 5-ethylpyridine, 6-ethylpyridine, 2,6-diethylpyridine, 2,4,6-triethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, 5-propylpyridine, 6 -propylpyridine, 2,6-dipropylpyridine, 2,4,6-tripropylpyridine, 2-butylpyridine, 3-butylpyridine, 4-butylpyridine, 5-butylpyridine, 6-butylpyridine, 2,6-dibutylpyridine, 2,4,6-tributylpyridine, 2-pentylpyridine, 3-pentylpyridine, 4-pentylpyridine, 5-pentylpyridine, 6-pentylpyridine, 2,6-dipentylpyridine, 2,4,6-tripentylpyridine, 2-hexylpyridine, 3-hexylpyridine , 4-hexylpyridine, 5-hexylpyridine, 6-hexylpyridine, 2-heptylpyridine, 3-heptylpyridine, 4-heptylpyridine, 5-heptylpyridine, 6-heptylpyridine, 2-octylpyridine, 3-octylpyridine, 4-octylpyridine, 5-octylpyridine, 6-octylpyridine, 2-nonylpyridine, 3-nonylpyridine, 4-nonylpyridine, 5-nonylpyridine, 6-nonylpyridine, 2-decylpyridine, 3-decylpyridine, 4-decylpyridine , 5-decylpyridine, 6-decylpyridine, 4-undecylpyridine, 4-dodecylpyridine, 4-tridecylpyridine, 4-tetradecylpyridine, 4-pentadecylpyridine, 4-hexadecylpyridine, 4-heptadecylpyridine, 4-octadecylpyridine, 4-nonadecylpyridine, 4-eicosylpyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 5-hydroxypyridine, 6-hydroxypyridine, 2,6-dihydroxypyridine, 2,4,The alkylpyridine may include, but is not limited to, at least one of 6-trihydroxypyridine, 2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine, 5-fluoropyridine, 6-fluoropyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 5-chloropyridine, 6-chloropyridine, 2,3-dichloropyridine, 2,3,6-trichloropyridine, 2,6-diamino-3,5-dinitropyridine, 2,6-diaminopyridine, 2,4,6-triaminopyridine, 2,4,6-trinitropyridine, 2,4,6-trichloropyridine, and 2,4,6-tribromopyridine, and is preferably a 4-alkylpyridine in the present invention.

[0205] In one specific embodiment of the present invention, pyridine is dissolved in a halogenated alkane (e.g., carbon tetrachloride), which is an organic solvent, and the solution is added dropwise to the halogenated polymer solution to carry out an ionization reaction in the presence of a protective gas, the reaction temperature being 60 to 150°C, preferably 80 to 120°C, and the reaction time being 4 to 20 hours, preferably 6 to 16 hours.

[0206] According to the present invention, the molar ratio of the pyridine to the halogen is 0.8 to 1.5:1, preferably 0.9 to 1.2:1.

[0207] In the present invention, when the ionization reaction has progressed to a certain extent, the solid insoluble matter is precipitated from the organic solvent, and after the reaction is completed, the solvent is separated, and the insoluble ionic polymer is washed with hexane once or twice and then vacuum dried to obtain the isobutylene-based pyridine salt ionic polymer described in the present invention.

[0208] A third aspect of the present invention provides an isobutylene-based cationic salt ionic polymer prepared by the above preparation method.

[0209] In the present invention, depending on the type of cationic salt-containing compound, the isobutylene-based cationic salt ionic polymer may be an isobutylene-based quaternary ammonium salt ionic polymer, an isobutylene-based quaternary phosphonium salt ionic polymer, an isobutylene-based imidazole salt ionic polymer, or an isobutylene-based pyridine salt ionic polymer.

[0210] A fourth aspect of the present invention provides the use of the above-mentioned isobutylene-based cationic salt ionic polymer as an antibacterial agent.

[0211] A fifth aspect of the present invention provides the use of the isobutylene-based cationic salt ionic polymer described above in inhibiting and killing at least one of bacteria, fungi, and viruses.

[0212] In the present invention, the types of bacteria, fungi, or viruses that the isobutylene-based cationic salt ionic polymer effectively inhibits and kills vary depending on the type of cationic salt in the isobutylene-based cationic salt ionic polymer.

[0213] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary ammonium salt ionic polymer, and the isobutylene-based quaternary ammonium salt ionic polymer is capable of inhibiting and killing bacteria.

[0214] In particular, said bacteria are selected from gram-negative and / or gram-positive bacteria.

[0215] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary phosphonium salt ionic polymer, and the isobutylene-based quaternary phosphonium salt ionic polymer is capable of inhibiting and killing at least one of bacteria, fungi, and viruses.

[0216] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based imidazole salt ionic polymer, and the isobutylene-based imidazole salt ionic polymer is capable of inhibiting and killing bacteria and / or fungi.

[0217] Specifically, the bacteria are anaerobic bacteria, and the fungi are molds.

[0218] In one particular embodiment of the present invention, the isobutylene-based cation salt ionic polymer is an isobutylene-based pyridine salt ionic polymer, and the isobutylene-based pyridine salt ionic polymer is capable of inhibiting and killing at least one of bacteria, fungi, and viruses.

[0219] A sixth aspect of the present invention provides a polymer material, characterized in that the antibacterial polymer material contains the above-mentioned isobutylene-based cation salt ionic polymer.

[0220] In the present invention, the T of the isobutylene-based cationic salt ionic polymer 5wt% The thermal weight loss temperature reaches above 170°C, which meets the requirements for the thermal processing of general polymer materials, and can be used as an antibacterial agent in the preparation of antibacterial polymer materials. According to the present invention, the amount of the isobutylene-based cationic salt ionic polymer used is 1 to 10 parts, preferably 2 to 7 parts, based on 100 parts of the polymer material.

[0221] In the present invention, when the above-mentioned isobutylene-based cationic salt ionic polymer is used to prepare an antibacterial polymer material, there is no migration or release of the antibacterial agent, and further, efficient, stable, low-toxicity, safe, and durable antibacterial and bacteriostatic effects are ensured.

[0222] According to the present invention, the polymer material is at least one selected from plastic, rubber, fiber, and paint.

[0223] In one specific embodiment of the present invention, when the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary ammonium salt ionic polymer, the amount of the isobutylene-based quaternary ammonium salt ionic polymer used is 1 to 10 parts, preferably 5 to 7 parts, per 100 parts of the polymer material.

[0224] In one specific embodiment of the present invention, when the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary phosphonium salt ionic polymer, the amount of the isobutylene-based quaternary phosphonium salt ionic polymer used is 1 to 8 parts, preferably 2 to 6 parts, per 100 parts of the polymer material.

[0225] In one specific embodiment of the present invention, when the isobutylene-based cation salt ionic polymer is an isobutylene-based imidazole salt ionic polymer, the amount of the isobutylene-based imidazole salt ionic polymer used is 1 to 10 parts, preferably 3 to 7 parts, per 100 parts of polymer material.

[0226] In one specific embodiment of the present invention, when the isobutylene-based cation salt ionic polymer is an isobutylene-based pyridine salt ionic polymer, the amount of the isobutylene-based pyridine salt ionic polymer used is 1 to 10 parts, preferably 3 to 7 parts, per 100 parts of polymer material.

[0227] The present invention will be described in detail below with reference to examples.

[0228] The content of each structural unit, benzyl bromide, and cation salt (quaternary ammonium salt, quaternary phosphonium salt, imidazole salt, pyridine salt) in the polymer was measured at room temperature using a Bruker AVANCE400 nuclear magnetic resonance spectrometer (Switzerland) at a magnetic field strength of 9.40 Tesla, deuterated chloroform (CDCL3) or deuterated dimethyl sulfoxide (DMSO) as the solvent, and tetramethylsilane (TMS) as the internal standard.

[0229] The molecular weight and distribution of the polymer were measured using a Shimadzu LC-20A gel permeation chromatography (GPC) and two Tosoh TSKgel GMH HR-H(30) columns connected in series, and a calibration curve was prepared using polystyrene as the standard.

[0230] The contents of metal elements in the polymer were measured by inductively coupled plasma optical emission spectroscopy (ICP-OES) according to the practice standard JYT015-1996.

[0231] The thermal decomposition temperature and thermal weight loss of the polymer were measured using a METTLER TGA / DSC1 model instrument with a test temperature range of 25–600°C, a heating rate of 10°C / min, and a nitrogen atmosphere of 50 mL / min. Specific Embodiment I

[0232] The physical and chemical parameters of the isobutylene-p-methylstyrene random copolymer used in the following examples and comparative examples are shown in Table 1, and its preparation method may refer to patent CN104558357B. [Table 1]

[0233] All other raw materials used in the following examples and comparative examples are commercially available products. Example I-1

[0234] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 32 g of polymer P1 (here, the content of p-methylstyrene structural units was 0.077 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and then 6.5 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 4 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 30 mL of carbon tetrachloride. The photobromination reaction was carried out by irradiation with a 595 nm LED light source, with a light source power of 80 W and a pulse time of 10 s. The light source was turned on and liquid bromine was slowly added dropwise. The bromination reaction was continued under irradiation of the pulsed light source until the addition of liquid bromine was complete. The reaction continued for 3 to 5 min, and when the color of the colloid turned light yellow, the light source was turned off and the reaction was stopped. After a bromination reaction time of approximately 120 min, brominated polymer solution XP-I-1 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble precipitate. The supernatant was vacuum dried at 40°C to a constant weight, and the colloid concentration was measured to be 14.3 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of side-group benzyl bromide in the reaction mixture was 11.4 mol% (benzyl bromination rate 71.7%). Since the main chain tertiary carbon hydrogen was converted to tertiary carbon bromine by the bromine substitution reaction, no characteristic peaks were observed in the nuclear magnetic hydrogen spectroscopy. (See Figure 1a.) 1 In the 1 H-NMR spectrum, the characteristic peak at the chemical shift of 4.4654 ppm was that of the side group benzyl bromide. (2) Ionization reaction The brominated polymer solution XP-I-1 was centrifuged to remove insoluble solids, and 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant temperature oil bath. N,N-dimethyltetradecylamine (Formula 6, where R3 and R4 are methyl, and R5 is C 14A 4 mL solution of 4-methyl-2-isopropyl-2-methylpropanol (4 mL, dissolved in 5 mL of dichloromethane) was added to the mixture, resulting in a 1.1:1 molar ratio of tertiary amine to liquid bromine. The mixture was then reacted under nitrogen protection at 60°C for 4 hours. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and vacuum dried at 40°C until the desired weight was obtained: isobutylene-based quaternary ammonium salt ionic polymer AI-1. As shown in Figure 1b, the content of quaternary ammonium salt functional groups was measured using nuclear magnetic hydrogen spectroscopy. The signal peak (4.4654 ppm) of the side group benzyl bromide disappeared, and all of it was converted to benzyl quaternary ammonium salt. The content of main chain tertiary carbon quaternary ammonium salt functional groups could be calculated from the area integral of the methyl peak in N,N-dimethyltetradecylamine. The measurement results showed that the total content of quaternary ammonium salt functional groups was 15.3 mol%, and the content of side group benzyl quaternary ammonium salt functional groups was 11.4 mol%. Therefore, the content of main chain tertiary carbon quaternary ammonium salt functional groups was calculated to be 3.9 mol%. As shown in Figure 1b 1 In the H-NMR spectrum, the characteristic peaks at chemical shifts of 3 to 4 ppm were characteristic peaks of the methyl signals in the quaternary ammonium salt functional group, and the characteristic peaks at chemical shifts of 4.5 to 5.5 ppm were characteristic peaks of the methylene signals in the benzyl quaternary ammonium salt functional group. As a result of measurement, analysis and calculation, the isobutylene-based quaternary ammonium salt ionic polymer AI-1 contains 12.6 mol % of structural units A, 3.3 mol % of structural units B, and 84.1 mol % of structural units C. The thermal weight loss analysis data for the isobutylene-p-methylstyrene copolymer PI-1, the brominated isobutylene-p-methylstyrene copolymer XP-I-1, and the isobutylene-based quaternary ammonium salt ionic polymer AI-1 are shown in Table 2, and the thermal weight loss graphs are shown in Figures 1c, 1d, and 1e, respectively. As can be seen from Figure 1c, the thermal weight loss of the isobutylene-p-methylstyrene copolymer PI-1 had only one stage (one step), the thermal weight loss temperature was approximately 402.3°C, and the weight loss rate was 100 wt%. As can be seen from Figure 1d, the brominated isobutylene-p-methylstyrene copolymer XP-I-1 exhibited two thermal weight loss stages (two steps). The first stage was located at approximately 342.2 °C, with a weight loss rate of 40.2 wt%, due to thermal decomposition of the carbon-bromine groups. The second stage was located at approximately 420.2 °C, with a weight loss rate of 53.1 wt%, due to thermal decomposition of the polymer backbone structure, which is consistent with that of PI-1. As can be seen in Figure 1e, the isobutylene-based quaternary ammonium salt ionic polymer AI-1 exhibited two thermal weight loss stages (two steps). The first stage was centered at approximately 219.8 °C, with a weight loss rate of 34.4 wt%, and was attributed to thermal decomposition of the quaternary ammonium salt functional groups. The second stage was centered at approximately 408.6 °C, with a weight loss rate of 64.6 wt%, and was attributed to thermal decomposition of the polymer backbone structure. This is consistent with that of PI-1. Since there was no stage of thermal decomposition of the carbon-bromine groups in XP-I-1, it was confirmed that all the carbon-bromine groups were ionized by the quaternary ammonium salt. The 5 wt% thermal weight loss temperature of the isobutylene-based quaternary ammonium salt ionic polymer AI-1 was 191.3 °C. [Table 2] Example I-2

[0235] An isobutylene-based quaternary ammonium salt ionic polymer was prepared according to the method of Example I-1 with the following exceptions. In step (2), 2 mL of N,N-dimethyltetradecylamine (in Formula 6, R3 and R4 are methyl, and R5 is C 14(linear alkyl group) and 2 mL of N,N-dimethyldecylamine (in Formula 6, R3 and R4 are methyl, and R5 is a C8 linear alkyl group) (dissolved in 5 mL of dichloromethane) were added to make the molar ratio of tertiary amine to liquid bromine 1.1:1, and the reaction was carried out under nitrogen protection at 60°C for 4 hours. A complex isobutylene-based quaternary ammonium salt ionic polymer AI-2 was obtained. As a result of the measurement, in the isobutylene-based quaternary ammonium salt ionic polymer AI-2, the total content of quaternary ammonium salt functional groups was 15.3 mol%, and the content of side group benzyl quaternary ammonium salt functional groups was 11.4 mol%.From these, the content of main chain quaternary ammonium salt functional groups was calculated to be 3.9 mol%. As a result of measurement, analysis and calculation, the isobutylene-based quaternary ammonium salt ionic polymer AI-2 contains 12.6 mol % of structural units A, 3.3 mol % of structural units B, and 84.1 mol % of structural units C. Example I-3

[0236] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 32 g of polymer PI-1 (here, the content of p-methylstyrene structural units was 0.077 mol) was dissolved in a mixed solvent of n-hexane (60 mL) and dichloromethane (100 mL), and then 10 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.5, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 6 mL of liquid bromine was drawn up with a pipette and added to a constant-pressure dropping funnel (light-shielded) containing 40 mL of dichlorohexane mixed solvent. The photobromination reaction was carried out by irradiation with a 630 nm LED light source at a light power of 60 W and a pulse time of 15 s. The light source was turned on and the bromination reaction was carried out under irradiation of the pulsed light source while controlling the dripping rate of the liquid bromine slowly. After the dripping of the liquid bromine was completed, the reaction was continued for 3 to 5 min. When the color of the colloid turned light yellow, the light source was turned off and the reaction was stopped. After a bromination reaction time of approximately 180 min, a brominated polymer solution XP-I-2 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 15.3 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 13.6 mol% (benzyl bromination rate 85.8%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-I-2 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 4.5 mL of triethylamine (Equation 6, where R3, R4, and R5 are all ethyl) (dissolved in 5 mL of dichloromethane) was added to achieve a 1.5:1 molar ratio of tertiary amine to liquid bromine. The reaction was carried out at 60 °C for 5 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary ammonium salt ionic polymer AI-3. As a result of the measurement, in the isobutylene-based quaternary ammonium salt ionic polymer AI-3, the total content of quaternary ammonium salt functional groups was 22.4 mol%, and the content of side group benzyl quaternary ammonium salt functional groups was 13.6 mol%.From these, it was calculated that the content of main chain quaternary ammonium salt functional groups was 8.8 mol%. As a result of measurement, analysis and calculation, the isobutylene-based quaternary ammonium salt ionic polymer AI-3 contains 14.7 mol % of structural units A, 1.2 mol % of structural units B, and 84.1 mol % of structural units C. Example I-4

[0237] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer PI-2 (where the content of p-methylstyrene structural units was 0.067 mol) was dissolved in a mixed solvent of n-hexane (60 mL) and dichloromethane (100 mL), and then 7 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.2, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 4 mL of liquid bromine was drawn up with a pipette and added to a constant-pressure dropping funnel (light-shielded) containing 30 mL of dichloromethane solvent. The bromination method described in Example 1 was used to obtain brominated polymer solution XP-I-3, except that the light source power was 60 W, the pulse time was 15 s, and the bromination reaction time was approximately 140 min. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 16.1%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 10.1 mol% (benzyl bromination rate 82.8%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-I-3 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 3 mL of N,N-dimethyloctylamine (Equation 6, where R3 and R4 are methyl, and R5 is a C8 linear alkyl group) (dissolved in 5 mL of dichloromethane) was added to the flask, resulting in a 1:1 molar ratio of tertiary amine to liquid bromine. The mixture was then reacted at 60 °C for 4 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary ammonium salt ionic polymer AI-4. As a result of the measurement, in the isobutylene-based quaternary ammonium salt ionic polymer AI-4, the total content of quaternary ammonium salt functional groups was 13.5 mol%, and the content of side group benzyl quaternary ammonium salt functional groups was 10.1 mol%.From these, the content of main chain quaternary ammonium salt functional groups was calculated to be 3.4 mol%. As a result of measurement, analysis and calculation, the isobutylene-based quaternary ammonium salt ionic polymer AI-4 contains 11.8 mol % of structural units A, 0.4 mol % of structural units B, and 87.8 mol % of structural units C. Example I-5

[0238] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer PI-3 (here, the content of p-methylstyrene structural units was 0.052 mol) was dissolved in a mixed solvent of n-hexane (60 mL) and dichloromethane (100 mL), and 5.8 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.3, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 3.5 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 20 mL of dichlorohexane solvent. Using the bromination method described in Example 1, brominated polymer solution XP-I-4 was obtained after a bromination reaction time of approximately 100 min. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 16.7 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 8.3 mol% (benzyl bromination rate 90.2%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-I-4 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 3.7 mL of tributylamine (Equation 6, where R3, R4, and R5 are n-butyl) (dissolved in 5 mL of dichloromethane) was added to achieve a 1.1:1 molar ratio of tertiary amine to liquid bromine, and the reaction was carried out at 60 °C for 4 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary ammonium salt ionic polymer AI-5. As a result of the measurement, in the isobutylene-based quaternary ammonium salt ionic polymer AI-5, the total content of quaternary ammonium salt functional groups was 11.1 mol%, the content of side group benzyl quaternary ammonium salt functional groups was 8.3 mol%, and the content of main chain quaternary ammonium salt functional groups was calculated to be 2.8 mol%. As a result of measurement, analysis and calculation, the isobutylene-based quaternary ammonium salt ionic polymer AI-5 contains 8.7 mol % of structural unit A, 0.5 mol % of structural unit B, and 90.8 mol % of structural unit C. Example I-6

[0239] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer PI-3 (here, the content of p-methylstyrene structural units was 0.052 mol) was dissolved in a mixed solvent of cyclohexane (80 mL) and carbon tetrachloride (80 mL), and 3.6 g of solid sodium bicarbonate powder was added. The molar content of the structural units provided by p-methylstyrene was 1:0.8, and the molar ratio of polymer to liquid bromine was 1:0.8. The bromination reaction was carried out in a light-shielded laboratory. 2.4 mL of liquid bromine was drawn up with a pipette and added to a constant-pressure dropping funnel (light-shielded) containing 20 mL of carbon tetrachloride solvent. The bromination method described in Example 1 was used, except that the light source power was 50 W and the bromination reaction time was approximately 80 min, to obtain brominated polymer solution XP-I-5. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 14.8%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 5.1 mol% (benzyl bromination rate 55.4%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-I-5 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 1.3 mL of N,N-dimethylphenylamine (Equation 6, where R3 and R4 are methyl, and R5 is phenyl) (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.1:1 molar ratio of tertiary amine to liquid bromine. The reaction was refluxed at 80°C for 8 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming insoluble colloidal particles. After the reaction was complete, the colloidal particles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40°C to a predetermined weight, yielding the isobutylene-based quaternary ammonium salt ionic polymer AI-6. As a result of the measurement, in the isobutylene-based quaternary ammonium salt ionic polymer AI-6, the total content of quaternary ammonium salt functional groups was 6.5 mol%, and the content of side group benzyl quaternary ammonium salt functional groups was 5.1 mol%.From these, it was calculated that the main chain quaternary ammonium salt functional groups were 1.4 mol%. As a result of measurement, analysis and calculation, the isobutylene-based quaternary ammonium salt ionic polymer AI-6 contains 5.7 mol % of structural unit A, 3.5 mol % of structural unit B, and 90.8 mol % of structural unit C. Example I-7

[0240] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer PI-4 (here, the content of p-methylstyrene structural units was 0.041 mol) was dissolved in a mixed organic solvent of cyclohexane (80 mL) and carbon tetrachloride (80 mL), and 5.2 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.5, based on the molar content of the structural units provided by p-methylstyrene. 3.2 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 30 mL of carbon tetrachloride solvent. The photobromination reaction was carried out by irradiating a 630 nm LED light source with a light source power of 40 W and a pulse time of 20 s. The light source was turned on and the liquid bromine was slowly added dropwise. The bromination reaction continued under pulsed light source irradiation until the addition of the liquid bromine was complete. The light source was then turned off to terminate the reaction. After approximately 140 min of bromination, the brominated polymer solution XP-I-6 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 14.1 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 5.2 mol% (benzyl bromination rate 74.2%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-I-6 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 1.5 mL of N,N-dimethylphenylamine (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.1:1 molar ratio of tertiary amine to liquid bromine, and the mixture was reacted at 80 °C for 8 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming insoluble colloidal particles. After the reaction was complete, the colloidal particles were separated from the solvent, washed twice with hexane, filtered, and then vacuum-dried at 40 °C to a predetermined weight to obtain the isobutylene-based quaternary ammonium salt ionic polymer AI-7. The content of quaternary ammonium salt functional groups was measured by nuclear magnetic hydrogen spectroscopy. It was found that some of the benzyl bromide was converted to quaternary ammonium salts, and the total content of quaternary ammonium salt functional groups was 8.7 mol%, the content of side-group benzyl quaternary ammonium salt functional groups was 5.2 mol%, and the content of main-chain tertiary carbon quaternary ammonium salt functional groups was 3.5 mol%. The isobutylene-based quaternary ammonium salt ionic polymer AI-7 contains 6.5 mol % of structural units A, 0.5 mol % of structural units B, and 93 mol % of structural units C. Comparative example I-1

[0241] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 32 g of polymer PI-1 (here, the content of p-methylstyrene structural units was 0.077 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), followed by the addition of 4.1 g of sodium carbonate powder. The molar ratio of polymer to liquid bromine was 1:1, based on the molar content of the structural units provided by p-methylstyrene. Using a pipette, 4 mL of liquid bromine was added in two 2 mL portions to a constant-pressure dropping funnel containing 15 mL of carbon tetrachloride (light-shielded). The photobromination reaction was carried out by irradiating the liquid with a 595 nm LED light source at 80 W. The liquid bromine solution in the constant-pressure dropping funnel was added all at once to the polymer solution, and the light source was turned on to initiate the bromination reaction. The bromination reaction produced intense smoke, but the large amount of HBr produced could not be neutralized. After 10 min of bromination, the colloidal system faded, at which point the light source was turned off to terminate the reaction. 100 mL of a 0.1 wt % aqueous NaOH solution was added to neutralize the HBr, yielding a brominated polymer solution XDP-I-1. Five ml of the above bromination reaction solution was vacuum dried at 40°C to a predetermined weight, and measurement by nuclear magnetic hydrogen spectroscopy revealed that the benzyl bromide content was only 1.1 mol% (benzyl bromination rate 6.9%), which is not only an extremely low bromination rate, but also contains a large amount of brominated n-hexane. (2) Ionization reaction 50 g of the supernatant of the brominated polymer solution XDP-I-1 was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant temperature oil bath. N,N-dimethyltetradecylamine (in Formula 6, R3 and R4 are methyl, and R5 is C 14 4 mL of a tertiary amine (linear alkyl group) (dissolved in 5 mL of dichloromethane) was added, and the molar ratio of tertiary amine to liquid bromine was adjusted to 1.1:1. The reaction was carried out under nitrogen protection at 60°C for 4 hours. After the reaction was completed, the insoluble micelles were separated from the solvent by filtration, washed twice with acetone, and filtered. The solids were then removed and dried in vacuum at 40°C to a predetermined weight to obtain isobutylene-based quaternary ammonium salt ionic polymer DI-1. The content of quaternary ammonium salt functional groups was measured by nuclear magnetic hydrogen spectroscopy, and it was found that all of the benzyl bromide was converted to quaternary ammonium salt, the total content of quaternary ammonium salt functional groups was 1.1 mol%, the content of side-group benzyl quaternary ammonium salt functional groups was 1.1 mol%, and the main chain contained no tertiary carbon quaternary ammonium groups. As a result of measurement, analysis and calculation, the isobutylene-based quaternary ammonium salt ionic polymer DI-1 contains 1.1 mol % of structural unit A, 14.8 mol % of structural unit B, and 84.1 mol % of structural unit C. Test Example I

[0242] The isobutylene-based quaternary ammonium salt polymer prepared in Example I-1 was blended with LDPE to produce an antibacterial plastic, and the antibacterial properties of the antibacterial plastic were tested using Escherichia coli as a gram-negative bacterium and Staphylococcus aureus as a gram-positive bacterium. Using a Polylab OS PTW 16 / 40 twin-screw extruder, an isobutylene-based quaternary ammonium salt polymer and LDPE resin were mixed in a mass ratio of 2:8, melt-extruded at 135°C, and granulated to prepare a 20% antibacterial masterbatch. Subsequently, the antibacterial masterbatch and LDPE resin were mixed in various ratios, melt-extruded in a twin-screw extruder, and granulated to produce antibacterial plastics with mass contents of isobutylene-based quaternary ammonium salt polymer of 1 wt%, 3 wt%, 5 wt%, 7 wt%, and 10 wt%, respectively. Each antibacterial plastic pellet was press-molded at 130°C and 20 MPa for 3 minutes, then cold-pressed at 15 MPa for 10 minutes to obtain a 1 mm thick experimental sheet. After leaving it for 24 hours, the sheet was cut into 20 mm x 20 mm test samples. (1) The samples were placed in a 6-well cell culture plate and sterilized by UV irradiation on both sides for 30 minutes. 1 × 10 6 A 30 μL drop of bacterial suspension (CFU / mL) was placed on the sample surface and covered with a sterilized cover glass disc. The suspension was then evenly distributed over the sample surface. The six-well cell culture plate was placed in a 37°C incubator and incubated at a relative humidity of over 90%. After 24 h, 2 mL of saline solution was added to each well of the six-well culture plate using a pipette gun to wash the sample surface. The plate was then sonicated for 1 min to disperse the bacterial suspension. 100 μL of the washing solution was then drawn up using a pipette gun and serially diluted with saline. The appropriate dilution ratio was selected and spread on a nutrient agar plate. The plate was then incubated in a 37°C incubator for 24 h. The plate with a colony count between 30 and 300 was selected, and the viable bacterial count on the sample surface was calculated, along with the antibacterial rate (R). The results are shown in Table I-3. R = [(AB) / A] × 100% A is the number of viable bacteria on the surface of a plastic sample to which no antibacterial agent was added, and B is the number of viable bacteria on the surface of an antibacterial plastic sample. [Table 3] (2) Six antibacterial plastic samples were weighed and placed in Erlenmeyer flasks. In accordance with GB / T16886.12-2005, deionized water was added at a rate of 0.1 g / mL. The samples were then placed in a 37°C water bath shaker and shaken at a speed of 150 r / min. The samples were then immersed for 15 and 30 days before being tested for antibacterial properties. The test methods were the same as above. The results after 15 days of immersion are shown in Table I-4, and the results after 30 days of immersion are shown in Table I-5. [Table 4] [Table 5] From the above results, it was found that when the isobutylene-based quaternary ammonium salt ionic polymer prepared in Example I-1 is blended with LDPE as an antibacterial agent to produce antibacterial plastic, if the amount used is 5 parts or more, a good antibacterial effect is obtained, with the 24-hour antibacterial rate against gram-negative and gram-positive bacteria reaching 70% or more, and the antibacterial plastic also shows good antibacterial effect when immersed in water for 15 to 30 days. Specific Embodiment II

[0243] The physical and chemical parameters of the isobutylene-p-methylstyrene random copolymer used in the following examples and comparative examples are shown in Table II-1, and its preparation method may refer to Patent CN104558357B. [Table 6]

[0244] All other raw materials used in the following examples and comparative examples were commercially available. Example II-1

[0245] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 32 g of polymer P-II-1 (here, the content of p-methylstyrene structural units was 0.077 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and then 6.5 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 4 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 30 mL of carbon tetrachloride. The photobromination reaction was carried out by irradiation with a 595 nm LED light source at a light power of 80 W and a pulse time of 10 s. The light source was turned on and the liquid bromine solution was slowly added dropwise. The bromination reaction was carried out under the irradiation of the pulsed light source. After the addition of the liquid bromine was completed, the reaction was continued for 3 to 5 min. When the color of the colloid turned light yellow, the light source was turned off and the reaction was stopped. After a bromination reaction time of approximately 120 min, the brominated polymer solution XP-II-1 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured and found to be 14.3 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of side-group benzyl bromide in the product was 11.4 mol% (benzyl bromination rate 71.7 wt%). Since the main-chain tertiary carbon hydrogen was converted to tertiary carbon bromine by the bromine substitution reaction, no characteristic peaks were observed in the nuclear magnetic hydrogen spectroscopy. 1 The H-NMR spectrum is shown in Figure 2a, and as can be seen from Figure 2a, the characteristic peak at the chemical shift of 4.4654 ppm was that of the side group benzyl bromide. (2) Ionization reaction After centrifuging the brominated polymer solution XP-II-1 to remove insoluble solids, 50 g of the resulting supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 3.8 g of triphenylphosphine (Eq. 7, where R6, R7, and R8 are phenyl) (dissolved in 10 mL of carbon tetrachloride) was added to achieve a 1:1 molar ratio of tertiary phosphine to liquid bromine. The mixture was refluxed at 80 °C for 16 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming a particle slurry. After the reaction was complete, the solid particles were separated from the solvent and washed twice with hexane. The solid particles were then removed and vacuum dried at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary phosphonium salt ionic polymer A-II-1. The content of quaternary phosphonium salts measured by nuclear magnetic hydrogen spectroscopy is shown in Figure 2b. As can be seen from Figure 2b, the signal peaks of the side-group benzyl bromide (4.4-4.6 ppm) have disappeared, and all of them have been converted to quaternary phosphonium salts. The total content of quaternary phosphonium salt functional groups, calculated by subtracting the content of benzene rings in the polymer backbone from the peak area integral of the benzene rings, was 15.2 mol%, the content of side-group benzyl quaternary phosphonium salt functional groups was 11.4 mol%, and the content of main-chain tertiary carbon quaternary phosphonium salt functional groups was 3.8 mol%. The characteristic peaks at chemical shifts of 4.7-5.7 ppm were characteristic peaks of methylene signals in the side-group benzyl quaternary phosphonium salt functional groups, and the characteristic peaks at chemical shifts of 7.3-8.3 ppm were characteristic peaks of the benzene ring signals of the quaternary phosphonium salts. The isobutylene-based quaternary phosphonium salt ionic polymer A-II-1 contains 12.6 mol % of structural units A, 3.3 mol % of structural units B, and 84.1 mol % of structural units C. The thermal weight loss analysis data for isobutylene-p-methylstyrene copolymer P-II-1, brominated isobutylene-p-methylstyrene copolymer XP-II-1, and isobutylene-based quaternary phosphonium salt ionic polymer A-II-1 are shown in Table II-2, and the thermal weight loss graphs are shown in Figures 2c, 2d, and 2e, respectively. As can be seen from Figure 2c, the thermal weight loss of the isobutylene-p-methylstyrene copolymer P-II-1 had only one stage (one step), the thermal weight loss temperature was approximately 402.3°C, and the weight loss rate was 100 wt%. As can be seen from Figure 2d, the brominated isobutylene-p-methylstyrene copolymer XP-II-1 exhibited two thermal weight loss stages (two steps). The first stage was located at approximately 342.2 °C, with a weight loss rate of 40.2 wt%, due to thermal decomposition of the carbon-bromine groups. The second stage was located at approximately 420.2 °C, with a weight loss rate of 53.1 wt%, due to thermal decomposition of the polymer backbone structure, consistent with that of XP-II-1. As can be seen in Figure 2e, the isobutylene-based quaternary phosphonium salt ionic polymer A-II-1 exhibited two thermal weight loss stages (two steps). The first stage was located at approximately 281.7 °C, with a weight loss rate of 47.4 wt%, and was attributed to the thermal decomposition of the quaternary phosphonium salt functional groups. The second stage was located at approximately 412.2 °C, with a weight loss rate of 49.3 wt%, and was attributed to the thermal decomposition of the polymer backbone structure. This is consistent with that of P-II-1. Since there was no stage in XP-II-1 where the carbon-bromine groups were thermally decomposed, it was confirmed that all the carbon-bromine groups were ionized by the quaternary phosphonium salt. The 5 wt% thermal weight loss temperature of the isobutylene-based quaternary phosphonium salt ionic polymer A-II-1 was 232.2 °C. [Table 7] Example II-2

[0246] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer P-II-2 (here, the content of p-methylstyrene structural units was 0.062 mol) was dissolved in a mixed organic solvent of cyclohexane (60 mL) and carbon tetrachloride (65 mL), followed by the addition of 6.5 g of sodium bicarbonate powder. The molar ratio of polymer to liquid bromine was 1:1.2, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 3.8 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 40 mL of carbon tetrachloride solvent. The photobromination reaction was carried out by irradiation with a 595 nm LED light source at a light power of 50 W and a pulse time of 15 s. The light source was turned on, and the liquid bromine solution was slowly added dropwise. The bromination reaction was carried out under irradiation of the pulsed light source until the addition of the liquid bromine was completed. After a bromination reaction time of about 130 min, a brominated polymer solution XP-II-2 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 16.7 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 9.4 mol% (benzyl bromination rate 82.5%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-II-2 to remove insoluble solids, 40 g of the resulting supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 3.6 g of triphenylphosphine (Equation 7, where R6, R7, and R8 are phenyl) (dissolved in 10 mL of carbon tetrachloride) was added to achieve a 1.1:1 molar ratio of tertiary phosphine to liquid bromine, and the mixture was refluxed at 80 °C for 12 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming a solid particle slurry. After the reaction was complete, the solid particles and solvent were separated by filtration, washed twice with hexane, and filtered. The solid particles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary phosphonium salt ionic polymer A-II-2. The content of quaternary phosphonium salt was measured by nuclear magnetic hydrogen spectroscopy. It was found that all of the benzyl bromide was converted to quaternary phosphonium salt, and the total content of quaternary phosphonium salt functional groups was 12.4 mol%, the content of side-group benzyl quaternary phosphonium salt functional groups was 9.4 mol%, and the content of main-chain tertiary carbon quaternary phosphonium salt functional groups was 3 mol%. As a result of measurement, analysis and calculation, the isobutylene-based quaternary phosphonium salt ionic polymer A-II-2 contains 9.7 mol % of structural units A, 1.7 mol % of structural units B, and 88.6 mol % of structural units C. Example II-3

[0247] An isobutylene-based quaternary phosphonium salt ionic polymer was prepared according to the method of Example II-2, with the following exceptions. After centrifuging the brominated polymer solution XP-II-2 to remove insoluble solids, 40 g of the resulting supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 4 g of tricyclohexylphosphine (Equation 7, where R6, R7, and R8 are all cyclohexyl) (dissolved in 10 mL of carbon tetrachloride) was added to achieve a 1.2:1 molar ratio of tertiary phosphine to liquid bromine. The mixture was refluxed at 80 °C for 16 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent, washed twice with hexane, and filtered. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary phosphonium salt ionic polymer A-II-3. The content of quaternary phosphonium salt was measured by nuclear magnetic hydrogen spectroscopy. It was found that all of the benzyl bromide was converted to quaternary phosphonium salt, and the total content of quaternary phosphonium salt functional groups was 12.4 mol%, the content of side-group benzyl quaternary phosphonium salt functional groups was 9.4 mol%, and the content of main-chain tertiary carbon quaternary phosphonium salt functional groups was 3 mol%. The isobutylene-based quaternary phosphonium salt ionic polymer A-II-3 contains 9.7 mol % of structural units A, 1.7 mol % of structural units B, and 88.6 mol % of structural units C. Example II-4

[0248] (1) Photobromination reaction In a 500 mL three-neck flask equipped with a magnetic stirrer, 25 g of polymer P-II-3 (here, the content of p-methylstyrene structural units was 0.035 mol) was dissolved in a mixed organic solvent of cyclohexane (60 mL) and carbon tetrachloride (60 mL), and 4 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.3, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 2.4 mL of liquid bromine was drawn up with a pipette and added to a constant-pressure dropping funnel (light-shielded) containing 15 mL of carbon tetrachloride solvent. Bromination was carried out according to the method in Example 1, and after a bromination reaction time of approximately 90 min, brominated polymer solution XP-II-3 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 14.6 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 7.8 mol% (benzyl bromination rate 90.7%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-II-3 to remove insoluble solids, 40 g of the resulting supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 2.7 g of triphenylphosphine (Equation 7, where R6, R7, and R8 are all phenyl) (dissolved in 10 mL of carbon tetrachloride) was added to achieve a 1.1:1 molar ratio of tertiary phosphine to liquid bromine, and the mixture was refluxed at 80 °C for 12 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming a solid particle slurry. After the reaction was complete, the solid particles and solvent were separated, washed twice with hexane, and filtered. The solid particles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary phosphonium salt ionic polymer A-II-4. The content of quaternary phosphonium salt was measured by nuclear magnetic hydrogen spectroscopy. It was found that all of the benzyl bromide was converted to quaternary phosphonium salt, and the total content of quaternary phosphonium salt functional groups was 10.6 mol%, the content of side-group benzyl quaternary phosphonium salt functional groups was 7.8 mol%, and the content of main-chain tertiary carbon quaternary phosphonium salt functional groups was 2.8 mol%. The isobutylene-based quaternary phosphonium salt ionic polymer A-II-4 contains 8 mol % of structural units A, 0.6 mol % of structural units B, and 91.4 mol % of structural units C. Example II-5

[0249] An isobutylene-based quaternary phosphonium salt ionic polymer was prepared according to the method of Example II-4, with the following exceptions. After centrifuging the brominated polymer solution XP-II-3 to remove insoluble solids, 40 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant-temperature oil bath. 3 mL of tributylphosphine (Equation 7, where R6, R7, and R8 are all butyl) (dissolved in 10 mL of carbon tetrachloride) was added to achieve a 1.2:1 molar ratio of tertiary phosphine to liquid bromine, and the mixture was refluxed at 60 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent, washed twice with hexane, and filtered. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary phosphonium salt ionic polymer A-II-5. The content of quaternary phosphonium salt was measured by nuclear magnetic hydrogen spectroscopy. It was found that all of the benzyl bromide was converted to quaternary phosphonium salt, and the total content of quaternary phosphonium salt functional groups was 10.6 mol%, the content of side-group benzyl quaternary phosphonium salt functional groups was 7.8 mol%, and the content of main-chain tertiary carbon quaternary phosphonium salt functional groups was 2.8 mol%. The isobutylene-based quaternary phosphonium salt ionic polymer A-II-5 contains 8 mol % of structural units A, 0.6 mol % of structural units B, and 91.4 mol % of structural units C. Example II-6

[0250] (1) Photobromination reaction In a 500 mL three-neck flask equipped with a magnetic stirrer, 25 g of polymer P-II-3 (here, the content of p-methylstyrene structural units was 0.035 mol) was added to a mixed organic solvent of n-heptane (62 mL) and carbon tetrachloride (62 mL), and 2.4 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:0.8, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 1.4 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 15 mL of carbon tetrachloride solvent. Bromination was carried out according to the method in Example 2, and after a bromination reaction time of approximately 60 min, brominated polymer solution XP-II-4 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 14.1 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 4.3 mol% (benzyl bromination rate: 50%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-II-4 to remove insoluble solids, 40 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 1.8 g of triphenylphosphine (Equation 7, where R6, R7, and R8 are all phenyl) (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.2:1 molar ratio of tertiary phosphine to liquid bromine, and the mixture was refluxed at 80 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming a solid particle slurry. After the reaction was complete, the solid particles and solvent were separated, washed twice with hexane, and filtered. The solid particles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary phosphonium salt ionic polymer A-II-6. The content of quaternary phosphonium salt was measured by nuclear magnetic hydrogen spectroscopy. It was found that all of the benzyl bromide was converted to quaternary phosphonium salt, and the total content of quaternary phosphonium salt functional groups was 5.7 mol%, the content of side-group benzyl quaternary phosphonium salt functional groups was 4.3 mol%, and the content of main-chain tertiary carbon quaternary phosphonium salt functional groups was 1.4 mol%. The isobutylene-based quaternary phosphonium salt ionic polymer A-II-6 contains 4.8 mol % of structural units A, 3.8 mol % of structural units B, and 91.4 mol % of structural units C. Example II-7

[0251] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 50 g of polymer P-II-4 (here, the content of p-methylstyrene structural units was 0.058 mol) was dissolved in a mixed organic solvent of cyclohexane (120 mL) and carbon tetrachloride (120 mL), and 7.6 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.5, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 4.5 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 50 mL of carbon tetrachloride solvent. The photobromination reaction was carried out by irradiation with a 630 nm LED light source at a light power of 40 W and a pulse time of 20 s. The light source was turned on, and liquid bromine was slowly added dropwise. The bromination reaction was carried out under irradiation of the pulsed light source until the addition of liquid bromine was completed. The light source was then turned off to stop the reaction. After a bromination reaction time of approximately 160 min, a brominated polymer solution XP-II-5 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 13.6 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 5.1 mol% (benzyl bromination rate 72.8%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-II-5 to remove insoluble solids, 40 g of the resulting supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 2.2 g of triphenylphosphine (Equation 7, where R6, R7, and R8 are all phenyl) (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1:1 molar ratio of tertiary phosphine to liquid bromine, and the mixture was refluxed at 80 °C for 12 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming a solid particle slurry. After the reaction was complete, the solid particles and solvent were separated, washed twice with hexane, and filtered. The solid particles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based quaternary phosphonium salt ionic polymer A-II-7. Measurement of the quaternary phosphonium salt content by nuclear magnetic hydrogen spectroscopy revealed that most of the benzyl bromide was converted to quaternary phosphonium salt, with the total content of quaternary phosphonium salt functional groups being 8.8 mol%, the content of side-group benzyl quaternary phosphonium salt functional groups being 5.1 mol%, and the content of main-chain tertiary carbon quaternary phosphonium salt functional groups being 3.7 mol%. The isobutylene-based quaternary phosphonium salt ionic polymer A-II-7 contains 6.5 mol % of structural units A, 0.5 mol % of structural units B, and 93 mol % of structural units C. Comparative Example II-1

[0252] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 32 g of polymer P-II-1 (here, the content of p-methylstyrene structural units was 0.077 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), followed by the addition of 4.1 g of sodium carbonate powder. The molar ratio of polymer to liquid bromine was 1:1, based on the molar content of the structural units provided by p-methylstyrene. Using a pipette, 4 mL of liquid bromine was added in two 2 mL portions to a constant-pressure dropping funnel containing 15 mL of carbon tetrachloride (light-shielded). The photobromination reaction was carried out by irradiating the liquid with a 595 nm LED light source at 80 W. The liquid bromine solution in the constant-pressure dropping funnel was added all at once to the polymer solution, and the light source was turned on to initiate the bromination reaction. The bromination reaction produced intense smoke, but the large amount of HBr produced could not be neutralized. After 10 min of bromination, the colloidal system faded, at which point the light source was turned off to terminate the reaction. 100 mL of a 0.1 wt % aqueous NaOH solution was added to neutralize the HBr, yielding a brominated polymer solution XDP-II-1. Five ml of the above bromination reaction solution was vacuum dried at 40°C to a predetermined weight, and measurement by nuclear magnetic hydrogen spectroscopy revealed that the benzyl bromide content was only 0.98 mol% (benzyl bromination rate: 6.2%), which is not only an extremely low bromination rate, but also contains a large amount of brominated n-hexane. (2) Ionization reaction 50 g of the supernatant from the brominated polymer solution XDP-II-1 was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant-temperature oil bath. 4 g of triphenylphosphine (Equation 7, where R6, R7, and R8 are phenyl) (dissolved in 10 mL of carbon tetrachloride) was added to achieve a 1:1 molar ratio of tertiary phosphine to liquid bromine. The reaction was refluxed at 80 °C for 6 hours under nitrogen protection. After the reaction was complete, the insoluble micelles were separated from the solvent by filtration, washed twice with acetone, and filtered. The solids were removed and dried under vacuum at 40 °C to a predetermined weight to obtain the isobutylene-based quaternary phosphonium salt ionic polymer D-II-1. The content of quaternary phosphonium salt was measured by nuclear magnetic hydrogen spectroscopy, and it was found that all the benzyl bromide was converted to quaternary phosphonium salt, the total content of quaternary phosphonium salt functional groups was 1 mol%, the content of side benzyl quaternary phosphonium salt functional groups was 1 mol%, and the main chain contained no tertiary carbon quaternary phosphonium groups. As a result of measurement, analysis and calculation, the isobutylene-based quaternary phosphonium salt ionic polymer D-II-1 contains 1 mol % of structural unit A, 14.9 mol % of structural unit B, and 84.1 mol % of structural unit C. Test Example II

[0253] The isobutylene-based quaternary phosphonium salt polymer A-II-1 prepared in Example II-1 was blended with ABS resin to produce an antibacterial plastic, and the antibacterial properties of the antibacterial plastic were tested using Escherichia coli as a gram-negative bacterium and Staphylococcus aureus as a gram-positive bacterium. Using a Polylab OS PTW 16 / 40 twin-screw extruder, isobutylene-based quaternary phosphonium salt polymer A-II-1 and ABS resin were mixed in a mass ratio of 2:8, melt-extruded at 190°C, and granulated to prepare a 20 wt% antibacterial masterbatch. Subsequently, the antibacterial masterbatch and ABS resin were mixed in various ratios, melt-extruded in a twin-screw extruder, and granulated to produce antibacterial plastics with mass contents of isobutylene-based quaternary phosphonium salt polymer A-II-1 of 1 wt%, 2 wt%, 4 wt%, 6 wt%, and 8 wt%, respectively. Each antibacterial plastic pellet was press-molded at 200°C and 20 MPa for 3 minutes, then cold-pressed at 15 MPa for 10 minutes to obtain a 1 mm thick experimental sheet. After leaving it for 24 hours, the sheet was cut into 20 mm x 20 mm test samples. (1) The samples were placed in a 6-well cell culture plate and sterilized by UV irradiation on both sides for 30 minutes. 1 × 10 6 A 30 μL drop of bacterial suspension (CFU / mL) was placed on the sample surface and covered with a sterilized cover glass disc. The suspension was then evenly distributed over the sample surface. The six-well cell culture plate was placed in a 37°C incubator and incubated at a relative humidity of over 90%. After 24 h, 2 mL of saline solution was added to each well of the six-well culture plate using a pipette gun to wash the sample surface. The plate was then sonicated for 1 min to disperse the bacterial suspension. 100 μL of the washing solution was then drawn up using a pipette gun and serially diluted with saline. The appropriate dilution ratio was selected and spread on a nutrient agar plate. The plate was then incubated in a 37°C incubator for 24 h. The plate with a colony count between 30 and 300 was selected, and the viable bacterial count on the sample surface was calculated, along with the antibacterial rate (R). The results are shown in Table II-3. R = [(AB) / A] × 100% A is the number of viable bacteria on the surface of a plastic sample to which no antibacterial agent was added, and B is the number of viable bacteria on the surface of an antibacterial plastic sample. [Table 8] (2) Six antibacterial plastic samples were weighed and placed in Erlenmeyer flasks. In accordance with GB / T16886.12-2005, deionized water was added at a rate of 0.1 g / mL. The samples were then placed in a 37°C water bath shaker and shaken at a speed of 150 r / min. The samples were then immersed for 15 and 30 days before being tested for antibacterial properties. The test methods were the same as above. The results after 15 days of immersion are shown in Table II-4, and the results after 30 days of immersion are shown in Table II-5. [Table 9] [Table 10] The results in Tables II-3 to II-5 show that when the isobutylene-based quaternary phosphonium salt ionic polymer of the present invention is combined with ABS resin to produce an antibacterial plastic, if the amount added is 2 parts or more, it exhibits effective bactericidal and bacteriostatic properties, and even after immersion in water for 15 to 30 days, the bactericidal and bacteriostatic properties are still well maintained, resulting in an excellent sustained antibacterial effect. Specific Embodiment III

[0254] The physical and chemical parameters of the isobutylene-p-methylstyrene random copolymer used in the following examples and comparative examples are shown in Table III-1, and its preparation method may refer to Patent CN104558357B. [Table 11] All other raw materials used in the following examples and comparative examples were commercially available. Example III-1

[0255] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 30 g of polymer P-III-1 (here, the content of p-methylstyrene structural units was 0.074 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and then 6.4 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.1, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 4.2 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 30 mL of carbon tetrachloride. The photobromination reaction was carried out by irradiation with a 595 nm LED light source at a light power of 80 W and a pulse time of 10 s. The light source was turned on, and the liquid bromine solution was slowly added dropwise. The bromination reaction was carried out under irradiation of the pulsed light source until the addition of the liquid bromine was complete. The light source was then turned off to stop the reaction. After a bromination reaction time of approximately 120 min, a brominated polymer solution XP-III-1 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured and found to be 13.5 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of side-group benzyl bromide in the product was 12.3 mol% (benzyl bromination rate 75.9 wt%). Since the main-chain tertiary carbon hydrogen was converted to tertiary carbon bromine by the bromine substitution reaction, no characteristic peaks were observed in the nuclear magnetic hydrogen spectroscopy. 1 The H-NMR spectrum is shown in Figure 3a, and as can be seen from Figure 3a, the characteristic peak at the chemical shift of 4.4654 ppm was that of the side group benzyl bromide. (2) Ionization reaction After centrifuging the brominated polymer solution XP-III-1 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 2 mL of 1-butylimidazole (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.1:1 molar ratio of imidazole to liquid bromine, and the mixture was refluxed at 80 °C for 8 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming insoluble micelles. After the reaction was complete, the micelles were separated from the solvent, washed twice in hexane, and then vacuum-dried at 40 °C to a predetermined weight to obtain the isobutylene-based imidazole salt ionic polymer A-III-1. The imidazole salt content was measured by nuclear magnetic hydrogen spectroscopy, as shown in Figure 3b. As can be seen from Figure 3b, the signal peaks of the side group benzyl bromide (4.4-4.6 ppm) disappeared, and all of them were converted to imidazole salt. Based on the area integral of the signal peaks of the nitrogen ring (characteristic peaks with chemical shifts of 7.6-10.1 ppm), the total content of imidazole salt functional groups was calculated to be 16.4 mol%, the content of side group benzyl (characteristic peaks with chemical shifts of 5.1-5.9 ppm) imidazole salt functional groups was 12.3 mol%, and the content of main chain tertiary carbon imidazole salt functional groups was 4.1 mol%. The isobutylene-based imidazole salt ionic polymer A-III-1 contains 13.4 mol % of structural units A, 2.8 mol % of structural units B, and 83.8 mol % of structural units C. The thermal weight loss analysis data for isobutylene-p-methylstyrene copolymer P-III-1, brominated isobutylene-p-methylstyrene copolymer XP-III-1, and isobutylene-based imidazole salt ionic polymer A-III-1 are shown in Table III-2, and the thermal weight loss graphs are shown in Figures 3c, 3d, and 3e, respectively. As can be seen from Figure 3c, the thermal weight loss of the isobutylene-p-methylstyrene copolymer P-III-1 had only one stage (one step), the thermal weight loss temperature was approximately 402.3°C, and the weight loss rate was 100 wt%. As can be seen from Figure 3d, for the brominated isobutylene-p-methylstyrene copolymer XP-III-1, the thermal weight loss is concentrated in two stages (two steps). The first stage is concentrated at approximately 342.2 °C, with a weight loss rate of 40.2 wt%, due to thermal decomposition of the carbon-bromine groups. The second stage is concentrated at approximately 420.2 °C, with a weight loss rate of 53.1 wt%, due to thermal decomposition of the polymer main chain structure, which is consistent with P-III-1. As can be seen in Figure 3e, the thermal weight loss of the isobutylene-based imidazole salt ionic polymer A-III-1 was concentrated in two stages (two steps). The first stage was concentrated at approximately 280.2 °C, with a weight loss rate of 34.2 wt%, due to thermal decomposition of the imidazole salt functional groups. The second stage was concentrated at approximately 419.6 °C, with a weight loss rate of 56.9 wt%, due to thermal decomposition of the polymer backbone structure. This is consistent with P-III-1. Since there was no stage in XP-III-1 where the carbon-bromine groups were thermally decomposed, it was confirmed that all the carbon-bromine groups were ionized by the imidazole salt. The 5 wt% thermal weight loss temperature of the isobutylene-based imidazole salt ionic polymer A-III-1 was 233.7 °C. [Table 12] Example III-2

[0256] (1) Ionization reaction An isobutylene-based pyridine salt ionic polymer was prepared according to the method of Example III-1 with the following exceptions. After centrifuging the brominated polymer solution XP-III-1 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 1.6 mL of 1,2-dimethyl-5-nitroimidazole (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.1:1 molar ratio of imidazole to liquid bromine. Under nitrogen protection, the mixture was heated to 80 °C and refluxed for 8 hours. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and vacuum dried at 40 °C to a predetermined weight to obtain the isobutylene-based imidazole salt ionic polymer A-III-2. As a result of the measurement, in the isobutylene-based imidazole salt ionic polymer A-III-2, the total content of imidazole salt functional groups was 16.4 mol%, and the content of side group benzylimidazole salt functional groups was 12.3 mol%.From these, the content of main chain imidazole salt functional groups was calculated to be 4.1 mol%. As a result of measurement, analysis and calculation, the isobutylene-based imidazole salt ionic polymer A-III-2 contains 13.4 mol % of structural units A, 2.8 mol % of structural units B, and 83.8 mol % of structural units C. Example III-3

[0257] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 30 g of polymer P-III-2 (here, the content of p-methylstyrene structural units was 0.058 mol) was dissolved in a mixed organic solvent of cyclohexane (80 mL) and carbon tetrachloride (80 mL), and 7 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.4, based on the molar content of the structural units provided by p-methylstyrene. 4.2 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 30 mL of carbon tetrachloride solvent. The photobromination reaction was carried out by irradiating a 630 nm LED light source with a light source power of 60 W and a pulse time of 20 s. The light source was turned on and the liquid bromine was slowly added dropwise. The bromination reaction continued under pulsed light source irradiation until the addition of the liquid bromine was complete. The light source was then turned off to terminate the reaction. After approximately 130 min of bromination, the brominated polymer solution XP-III-2 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 13.2 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 9.7 mol% (benzyl bromination rate 78.9%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-III-2 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 2.3 mL of 1-butylimidazole (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.2:1 molar ratio of imidazole to liquid bromine, and the reaction was carried out at 80 °C for 12 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction process, forming insoluble colloidal particles. After the reaction was complete, the colloidal particles were separated from the solvent, washed twice with hexane, filtered, and then vacuum-dried at 40 °C to a predetermined weight to obtain the isobutylene-based imidazole salt ionic polymer A-III-3. Measurement of the imidazole salt content by nuclear magnetic hydrogen spectroscopy showed that part of the benzyl bromide was converted to imidazole salt, and the total content of imidazole salt functional groups was 15.9 mol%, the content of side-group benzylimidazole salt functional groups was 9.7 mol%, and the content of main-chain tertiary carbon imidazole salt functional groups was 6.2 mol%. The isobutylene-based imidazole salt ionic polymer A-III-3 contains 10.6 mol % of structural units A, 1.7 mol % of structural units B, and 87.7 mol % of structural units C. Example III-4

[0258] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer P-III-3 (here, the content of p-methylstyrene structural units was 0.052 mol) was dissolved in a mixed organic solvent of cyclohexane (80 mL) and carbon tetrachloride (100 mL), and 7 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.6, based on the molar content of the structural units provided by p-methylstyrene. 4.3 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (protected from light) containing 30 mL of carbon tetrachloride solvent. The photobromination reaction was carried out by irradiation with a 630 nm LED light source at a light source power of 60 W and a pulse time of 15 s. The light source was turned on, and liquid bromine was slowly added dropwise. The bromination reaction was carried out under irradiation of the pulsed light source until the addition of liquid bromine was completed. The light source was then turned off to stop the reaction. After a bromination reaction time of approximately 120 min, a brominated polymer solution XP-III-3 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 13.3 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 8.1 mol% (benzyl bromination rate 89%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-III-3 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 3.9 mL of 1-dodecyl imidazole (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.1:1 molar ratio of imidazole to liquid bromine, and the mixture was reacted at 80 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction process, forming insoluble colloidal particles. After the reaction was complete, the colloidal particles were separated from the solvent, washed twice with hexane, filtered, and then vacuum-dried at 40 °C to a predetermined weight to obtain the isobutylene-based imidazole salt ionic polymer A-III-4. Measurement of the imidazole salt content by nuclear magnetic hydrogen spectroscopy showed that all benzyl bromide was converted to imidazole salt, and the total content of imidazole salt functional groups was 13.9 mol%, the content of side-group benzylimidazole salt functional groups was 8.1 mol%, and the content of main-chain tertiary carbon imidazole salt functional groups was 5.8 mol%. The isobutylene-based imidazole salt ionic polymer A-III-4 contains 8.7 mol % of structural units A, 0.4 mol % of structural units B, and 90.9 mol % of structural units C. Example III-5

[0259] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer P-III-4 (here, the content of p-methylstyrene structural units was 0.039 mol) was dissolved in a mixed organic solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and 2.4 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:0.7, based on the molar content of the structural units provided by p-methylstyrene. 1.4 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (protected from light) containing 15 mL of carbon tetrachloride solvent. The photobromination reaction was carried out by irradiation with a 595 nm LED light source at a light source power of 50 W and a pulse time of 15 s. The light source was turned on, and liquid bromine was slowly added dropwise. The bromination reaction was carried out under irradiation of the pulsed light source until the addition of liquid bromine was complete. The light source was then turned off to stop the reaction. After a bromination reaction time of approximately 50 min, a brominated polymer solution XP-III-4 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 15.2 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 3.2 mol% (benzyl bromination rate: 48.5%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-III-4 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 0.9 mL of 1-butylimidazole (dissolved in 5 mL of carbon tetrachloride) was added to achieve a 1.2:1 molar ratio of imidazole to liquid bromine, and the reaction was carried out at 80 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction process, forming insoluble colloidal particles. After the reaction was complete, the colloidal particles were separated from the solvent, washed twice with hexane, filtered, and then vacuum-dried at 40 °C to a predetermined weight to obtain the isobutylene-based imidazole salt ionic polymer A-III-5. Measurement of the imidazole salt content by nuclear magnetic hydrogen spectroscopy revealed that all benzyl bromide was converted to imidazole salt, the total content of imidazole salt functional groups was 4.3 mol%, the content of side benzylimidazole salt functional groups was 3.2 mol%, and the content of main chain tertiary carbon imidazole salt functional groups was 1.1 mol%. The isobutylene-based imidazole salt ionic polymer A-III-5 contains 3.8 mol % of structural units A, 2.8 mol % of structural units B, and 93.4 mol % of structural units C. Comparative example III-1

[0260] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 30 g of polymer P-III-1 (here, the content of p-methylstyrene structural units was 0.074 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and then 3.6 g of sodium carbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.1, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. Using a pipette, 4.2 mL of liquid bromine was added in two 2.1 mL portions to a constant-pressure dropping funnel (light-shielded) containing 15 mL of carbon tetrachloride. The photobromination reaction was carried out by irradiating the mixture with a 595 nm LED light source at a power of 80 W. The liquid bromine solution in the constant pressure dropping funnel was added all at once to the polymer solution, and the light source was turned on to carry out the bromination reaction. The bromination reaction produced intense smoke, but the large amount of HBr produced could not be neutralized. After 10 minutes of bromination reaction, the colloidal system had faded, at which point the light source was turned off to stop the reaction. 100 mL of 0.1 wt% NaOH aqueous solution was added to neutralize the HBr, yielding the brominated polymer solution XDP-III-1. Five ml of the above bromination reaction solution was vacuum dried at 40°C to a predetermined weight, and measurement by nuclear magnetic hydrogen spectroscopy revealed that the benzyl bromide content was only 0.88 mol% (benzyl bromination rate: 5.4%), which is not only an extremely low bromination rate, but also contains a large amount of brominated n-hexane. (2) Ionization reaction 50 g of the supernatant of the brominated polymer solution XDP-III-1 was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant-temperature oil bath. 2 mL of 1-butylimidazole (dissolved in 5 mL of carbon tetrachloride) was added to adjust the molar ratio of pyridine to liquid bromine to 1.1:1, and the reaction was carried out at 80 °C for 10 hours under nitrogen protection. After the reaction was completed, the insoluble micelles were separated from the solvent by filtration, washed twice with acetone, and filtered. The solids were then removed and dried under vacuum at 40 °C to a predetermined weight to obtain the isobutylene-based pyridine salt ionic polymer D-III-1. The content of pyridine salt functional groups was measured by nuclear magnetic hydrogen spectroscopy, and it was found that all benzyl bromide was converted to imidazole salt, the total content of imidazole salt functional groups was 0.9 mol%, the content of side benzylimidazole salt functional groups was 0.9 mol%, and the main chain contained no tertiary carbon imidazole groups. As a result of measurement, analysis and calculation, the isobutylene-based imidazole salt ionic polymer D-III-1 contains 0.9 mol % of structural units A, 15.3 mol % of structural units B, and 83.8 mol % of structural units C. Test Example III

[0261] The isobutylene-based imidazole salt polymer prepared in Example III-1 was blended with ABS resin to produce an antibacterial plastic, and the antibacterial properties of the antibacterial plastic were tested using Penicillium as a fungus and Staphylococcus aureus as a bacterium. Using a Polylab OS PTW 16 / 40 twin-screw extruder, an isobutylene-based imidazole salt polymer and ABS resin were mixed in a mass ratio of 2:8, melt-extruded at 200°C, and granulated to prepare a 20% antibacterial masterbatch. Subsequently, the antibacterial masterbatch and ABS resin were mixed in various ratios, melt-extruded in a twin-screw extruder, and granulated to produce antibacterial plastics with mass contents of isobutylene-based imidazole salt polymer of 1 wt%, 3 wt%, 5 wt%, 7 wt%, and 10 wt%, respectively. Each antibacterial plastic pellet was press-molded at 200°C and 20 MPa for 3 minutes, then cold-pressed at 15 MPa for 10 minutes to obtain a 1 mm thick experimental sheet. After leaving it for 24 hours, the sheet was cut into 20 mm x 20 mm test samples. (1) The samples were placed in a 6-well cell culture plate and sterilized by UV irradiation on both sides for 30 minutes. 1 × 10 6 A 30 μL drop of bacterial suspension (CFU / mL) was placed on the sample surface, covered with a sterilized cover glass disc, and the bacterial suspension was evenly distributed across the sample surface. The six-well cell culture plate was placed in a 37°C incubator and incubated at a relative humidity of over 90%. After 24 h, 2 mL of saline solution was added to each well of the six-well culture plate using a pipette gun to wash the sample surface. The plate was then sonicated for 1 min to disperse the bacterial suspension. 100 μL of the washing solution was then drawn up using a pipette gun and serially diluted with saline. The appropriate dilution ratio was selected and spread on a nutrient agar plate. The plate was then incubated in a 37°C incubator for 24 h. The plate with a colony count between 30 and 300 was selected, and the viable bacterial count on the sample surface was calculated, along with the antibacterial rate (R). The results are shown in Table III-3. R = [(AB) / A] × 100% A is the number of viable bacteria on the surface of a plastic sample to which no antibacterial agent was added, and B is the number of viable bacteria on the surface of an antibacterial plastic sample. [Table 13] (2) Six antibacterial plastic samples were weighed and placed in Erlenmeyer flasks. In accordance with GB / T16886.12-2005, deionized water was added at a rate of 0.1 g / mL. The samples were then placed in a 37°C water bath shaker and shaken at a speed of 150 r / min. The samples were then immersed for 15 and 30 days before being tested for antibacterial properties. The test methods were the same as above. The results after 15 days of immersion are shown in Table III-4, and the results after 30 days of immersion are shown in Table III-5. [Table 14] [Table 15] From the above results, it was found that when the isobutylene-based imidazole salt ionic polymer prepared in Example III-1 is blended with ABS as an antibacterial agent to produce antibacterial plastic, when the amount used is 4 parts or more, good antibacterial properties are exhibited, and good antibacterial effects are maintained even after immersion in water for 15 to 30 days. Specific Embodiment IV

[0262] The physical and chemical parameters of the isobutylene-p-methylstyrene random copolymer used in the following examples and comparative examples are shown in Table IV-1, and its preparation method may refer to patent CN104558357B. [Table 16] All other raw materials used in the following examples and comparative examples were commercially available. Example IV-1

[0263] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 30 g of polymer P-IV-1 (here, the content of p-methylstyrene structural units was 0.075 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and then 7 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.1, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 4.2 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 30 mL of carbon tetrachloride. The photobromination reaction was carried out by irradiation with a 595 nm LED light source at a light power of 60 W and a pulse time of 10 s. The light source was turned on, and liquid bromine was slowly added dropwise. The bromination reaction was carried out under irradiation of the pulsed light source until the addition of liquid bromine was completed. The light source was then turned off to stop the reaction. After a bromination reaction time of approximately 130 min, a brominated polymer solution XP-IV-1 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble precipitate. The supernatant was vacuum dried at 40°C to a constant weight, and the colloid concentration was measured to be 13.4 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of side-group benzyl bromide in the reaction mixture was 12.8 mol% (benzyl bromination rate 77.6%). Since the main chain tertiary carbon hydrogen was converted to tertiary carbon bromine by the bromine substitution reaction, no characteristic peaks were observed in the nuclear magnetic hydrogen spectroscopy. (See Figure 4a.) 1 In the 1 H-NMR spectrum, the characteristic peak at the chemical shift of 4.4654 ppm was that of the side group benzyl bromide. (2) Ionization reaction The brominated polymer solution XP-IV-1 was centrifuged to remove insoluble solids, and 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant temperature oil bath. 15 is ethyl, and R 13 , R 14 , R 16 , R 17 (H) is hydrogen. 1.9 mL of bromine (dissolved in 5 mL of carbon tetrachloride) was added to the mixture, resulting in a molar ratio of pyridine to liquid bromine of 1.1:1. The mixture was then reacted at 80°C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction process, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and vacuum dried at 40°C to a predetermined weight, yielding isobutylene-based pyridine salt ionic polymer A-IV-1. The content of pyridine salt functional groups was measured using nuclear magnetic hydrogen spectroscopy, and the results are shown in Figure 4b. The signal peak (4.4654 ppm) of the side group benzyl bromide disappeared, and all of it was converted to benzyl pyridine salt. The total content of pyridine salt functional groups could be calculated from the peak area integral of the hydrogen on the pyridine ring in 4-ethylpyridine. The measurement results showed that the total content of pyridine salt functional groups was 17.5 mol%, and the content of side group benzyl pyridine salt functional groups was 12.8 mol%. Therefore, the content of main chain tertiary carbon pyridine salt functional groups was calculated to be 4.7 mol%, as shown in Figure 4b. 1 In the H-NMR spectrum, the characteristic peaks with chemical shifts of 7.9 to 9.7 ppm were characteristic peaks of the pyridine ring signals of the pyridine salt functional group, and the characteristic peaks with chemical shifts of 5.6 to 6.3 ppm were characteristic peaks of the methylene signals of the benzylpyridine salt functional group. As a result of measurement, analysis and calculation, the isobutylene-based pyridine salt ionic polymer A-IV-1 contains 14.3 mol % of structural units A, 2.2 mol % of structural units B, and 83.5 mol % of structural units C. The thermal weight loss analysis data for isobutylene-p-methylstyrene copolymer P-IV-1, brominated isobutylene-p-methylstyrene copolymer XP-IV-1, and isobutylene-based pyridine salt ionic polymer A-IV-1 are shown in Table IV-2, and the thermal weight loss graphs are shown in Figures 4c, 4d, and 4e, respectively. As can be seen from Figure 4c, the thermal weight loss of the isobutylene-p-methylstyrene copolymer P-IV-1 had only one stage (one step), the thermal weight loss temperature was approximately 402.3°C, and the weight loss rate was 100 wt%. As can be seen from Figure 4d, for the brominated isobutylene-p-methylstyrene copolymer XP-IV-1, the thermal weight loss was concentrated in two stages (two steps). The first stage was concentrated at approximately 342.2 °C, with a weight loss rate of 40.2 wt%, due to thermal decomposition of the carbon-bromine groups. The second stage was concentrated at approximately 420.2 °C, with a weight loss rate of 53.1 wt%, due to thermal decomposition of the polymer main chain structure, which is consistent with the isobutylene-p-methylstyrene copolymer P-IV-1. As can be seen in Figure 4e, the thermal weight loss of the isobutylene-based pyridine salt ionic polymer A-IV-1 was concentrated in two stages (two steps). The first stage was concentrated at approximately 280.5 °C, with a weight loss rate of 30.7 wt%, and was due to thermal decomposition of the pyridine salt functional groups. The second stage was concentrated at approximately 416.2 °C, with a weight loss rate of 60.0 wt%, and was due to thermal decomposition of the polymer backbone structure. This is consistent with P-IV-1. Since there was no stage in XP-IV-1 where the carbon-bromine groups were thermally decomposed, it was confirmed that all the carbon-bromine groups were ionized by the pyridine salt. The 5 wt% thermal weight loss temperature of the isobutylene-based pyridine salt ionic polymer A-IV-1 was 211.3 °C. [Table 17] Example IV-2

[0264] (2) Ionization reaction An isobutylene-based pyridine salt ionic polymer was prepared according to the method of Example IV-1 with the following exceptions. The brominated polymer solution XP-IV-1 was centrifuged to remove insoluble solids, and 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant temperature oil bath. 15 is methyl and R 13 , R 14 , R 16 , R 17(H) is hydrogen. 1.6 mL of bromine (dissolved in 5 mL of carbon tetrachloride) was added, and the molar ratio of pyridine to liquid bromine was adjusted to 1.1:1. Under nitrogen protection, the mixture was heated to 80°C and refluxed for 10 hours. The brominated polymer gradually precipitated from the solvent during the ionization reaction process, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and vacuum dried at 40°C to a predetermined weight to obtain isobutylene-based pyridine salt ionic polymer A-IV-2. As a result of the measurement, the content of pyridine salt functional groups in the isobutylene-based pyridine salt ionic polymer A-IV-2 was 17.5 mol%, and the content of side group benzylpyridine salt functional groups was 12.8 mol%.From these, the content of main chain pyridine salt functional groups was calculated to be 4.7 mol%. As a result of measurement, analysis and calculation, the isobutylene-based pyridine salt ionic polymer A-IV-2 contains 14.3 mol % of structural units A, 2.2 mol % of structural units B, and 83.5 mol % of structural units C. Example IV-3

[0265] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer P-IV-2 (here, the content of p-methylstyrene structural units was 0.075 mol) was dissolved in a mixed organic solvent of cyclohexane (80 mL) and carbon tetrachloride (80 mL), and 11 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.7, based on the molar content of the structural units provided by p-methylstyrene. 6.5 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (protected from light) containing 40 mL of carbon tetrachloride solvent. The photobromination reaction was carried out by irradiation with a 630 nm LED light source at a light source power of 50 W and a pulse time of 20 s. The light source was turned on, and liquid bromine was slowly added dropwise. The bromination reaction was carried out under irradiation of the pulsed light source until the addition of liquid bromine was completed. The light source was then turned off to stop the reaction. After a bromination reaction time of approximately 160 min, a brominated polymer solution XP-IV-2 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 15.1 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 12.4 mol% (benzyl bromination rate 73.8%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-IV-2 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 2.5 mL of pyridine (dissolved in 5 mL of carbon tetrachloride) was added to achieve a pyridine to liquid bromine molar ratio of 1.3:1, and the mixture was reacted at 80 °C for 12 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction process, forming insoluble colloidal particles. After the reaction was complete, the colloidal particles were separated from the solvent, washed twice with hexane, filtered, and then vacuum-dried at 40 °C to a predetermined weight to obtain the isobutylene-based pyridine salt ionic polymer A-IV-3. The content of pyridine salt functional groups was measured by nuclear magnetic hydrogen spectroscopy. It was found that part of the benzyl bromide was converted to pyridine salt, and the total content of pyridine salt functional groups was 21.6 mol %, the content of side-group benzylpyridine salt functional groups was 12.4 mol %, and the content of main-chain tertiary carbon pyridine salt functional groups was 9.2 mol %. The isobutylene-based pyridine salt ionic polymer A-IV-3 contains 13.2 mol % of structural units A, 0.6 mol % of structural units B, and 86.2 mol % of structural units C. Example IV-4

[0266] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 35 g of polymer P-IV-3 (here, the content of p-methylstyrene structural units was 0.057 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and 4.8 g of solid sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 3 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 20 mL of carbon tetrachloride solvent. Using the bromination method described in Example 1, brominated polymer solution XP-IV-3 was obtained after a bromination reaction time of approximately 70 min. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 15.4 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 7.3 mol% (benzyl bromination rate 71.6%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-IV-3 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 1.3 mL of 2-aminomethylpyridine (dissolved in 5 mL of carbon tetrachloride) was added to achieve a pyridine to liquid bromine molar ratio of 1.2:1, and the mixture was reacted at 80 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based pyridine salt ionic polymer A-IV-4. As a result of the measurement, in the isobutylene-based pyridine salt ionic polymer A-IV-4, the total content of pyridine salt functional groups was 9.5 mol%, the content of side group benzylpyridine salt functional groups was 7.3 mol%, and the calculated content of main chain pyridine salt functional groups was 2.2 mol%. As a result of measurement, analysis and calculation, the isobutylene-based pyridine salt ionic polymer A-IV-4 contains 8.4 mol % of structural units A, 1.8 mol % of structural units B, and 89.8 mol % of structural units C. Example IV-5

[0267] (1) Photobromination reaction The photobromination method of Example IV-4 was adopted, except that the molar content of the structural unit provided by p-methylstyrene was used, and the molar ratio of polymer to liquid bromine was 1:0.7. 2 mL of liquid bromine was drawn up with a pipette and added to a constant-pressure dropping funnel (protected from light) containing 20 mL of carbon tetrachloride solvent. After a bromination reaction time of approximately 40 min, brominated polymer solution XP-IV-4 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 15 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 4.8 mol% (benzyl bromination rate: 47.1%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-IV-4 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 1 mL of 2,3-dichloropyridine (dissolved in 5 mL of carbon tetrachloride) was added to achieve a pyridine to liquid bromine molar ratio of 1.4:1, and the mixture was reacted at 80 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based pyridine salt ionic polymer A-IV-5. As a result of the measurement, in the isobutylene-based pyridine salt ionic polymer A-IV-5, the total content of pyridine salt functional groups was 6.2 mol%, the content of side group benzylpyridine salt functional groups was 4.8 mol%, and the calculated content of main chain pyridine salt functional groups was 1.4 mol%. As a result of measurement, analysis and calculation, the isobutylene-based pyridine salt ionic polymer A5 contains 5.6 mol % of structural units A, 4.6 mol % of structural units B, and 89.8 mol % of structural units C. Example IV-6

[0268] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 40 g of polymer P-IV-4 (here, the content of p-methylstyrene structural units was 0.045 mol) was dissolved in a mixed solvent of n-hexane (100 mL) and carbon tetrachloride (100 mL), and then 4.6 g of sodium bicarbonate powder was added. The molar ratio of polymer to liquid bromine was 1:1.2, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. 2.8 mL of liquid bromine was pipetted and added to a constant-pressure dropping funnel (light-shielded) containing 20 mL of carbon tetrachloride. The photobromination reaction was carried out by irradiation with a 595 nm LED light source at a light power of 50 W and a pulse time of 15 s. The light source was turned on, and liquid bromine was slowly added dropwise. The bromination reaction was continued under irradiation of the pulsed light source until the addition of liquid bromine was completed. The light source was then turned off to stop the reaction. After a bromination reaction time of approximately 100 min, a brominated polymer solution XP-IV-5 was obtained. 10 ml of the bromination reaction solution was centrifuged to separate the insoluble solid precipitate, and the resulting supernatant was vacuum dried at 40°C to a constant weight. The colloid concentration was measured to be 14.5 wt%. Nuclear magnetic hydrogen spectroscopy revealed that the content of benzyl bromide side groups in the reaction mixture was 5.2 mol% (benzyl bromination rate 76.5%). (2) Ionization reaction After centrifuging the brominated polymer solution XP-IV-5 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 1.6 mL of 4-butylpyridine (dissolved in 5 mL of carbon tetrachloride) was added to achieve a pyridine to liquid bromine molar ratio of 1.2:1, and the mixture was reacted at 80 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based pyridine salt ionic polymer A-IV-6. As a result of the measurement, in the isobutylene-based pyridine salt ionic polymer A-IV-6, the total content of pyridine salt functional groups was 7.1 mol%, the content of side group benzylpyridine salt functional groups was 5.2 mol%, and the calculated content of main chain pyridine salt functional groups was 1.9 mol%. As a result of measurement, analysis and calculation, the isobutylene-based pyridine salt ionic polymer A-IV-6 contains 6.2 mol % of structural units A, 0.6 mol % of structural units B, and 93.2 mol % of structural units C. Example IV-7

[0269] The ionization reaction was carried out using the brominated polymer solution XP-IV-5 prepared in Example IV-6. (2) Ionization reaction After centrifuging the brominated polymer solution XP-IV-5 to remove insoluble solids, 50 g of the supernatant was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a thermostatic oil bath. 2.1 mL of 4-octylpyridine (dissolved in 5 mL of carbon tetrachloride) was added to achieve a pyridine to liquid bromine molar ratio of 1.1:1, and the mixture was reacted at 80 °C for 10 hours under nitrogen protection. The brominated polymer gradually precipitated from the solvent during the ionization reaction, forming clumped micelles. After the reaction was complete, the clumped micelles were separated from the solvent and washed twice with hexane. The micelles were then removed and dried under vacuum at 40 °C to a predetermined weight, yielding the isobutylene-based pyridine salt ionic polymer A-IV-7. As a result of the measurement, in the isobutylene-based pyridine salt ionic polymer A-IV-7, the total content of pyridine salt functional groups was 7.1 mol%, the content of side group benzylpyridine salt functional groups was 5.2 mol%, and the calculated content of main chain pyridine salt functional groups was 1.9 mol%. As a result of measurement, analysis and calculation, the isobutylene-based pyridine salt ionic polymer A-IV-7 contains 6.2 mol % of structural units A, 0.6 mol % of structural units B, and 93.2 mol % of structural units C. Comparative example IV-1

[0270] (1) Photobromination reaction In a 1000 mL three-neck flask equipped with a magnetic stirrer, 30 g of polymer P-IV-1 (here, the content of p-methylstyrene structural units was 0.075 mol) was dissolved in a mixed solvent of n-hexane (80 mL) and carbon tetrachloride (80 mL), and then 3.6 g of sodium carbonate powder was added. The molar ratio of polymer to liquid bromine was 1.1:1, based on the molar content of the structural units provided by p-methylstyrene. The bromination reaction was carried out in a light-shielded laboratory. Using a pipette, 4.2 mL of liquid bromine was added in two 2.1 mL portions to a constant-pressure dropping funnel (light-shielded) containing 15 mL of carbon tetrachloride. The photobromination reaction was carried out by irradiating the mixture with a 595 nm LED light source at a power of 80 W. The liquid bromine solution in the constant pressure dropping funnel was added all at once to the polymer solution, and the light source was turned on to carry out the bromination reaction. The bromination reaction produced intense smoke, but the large amount of HBr produced could not be neutralized. After 10 minutes of bromination reaction, the colloidal system had faded, at which point the light source was turned off to stop the reaction. 100 mL of 0.1 wt% NaOH aqueous solution was added to neutralize the HBr, yielding the brominated polymer solution XDP-IV-1. Five ml of the above bromination reaction solution was vacuum dried at 40°C to a predetermined weight, and measurement by nuclear magnetic hydrogen spectroscopy revealed that the benzyl bromide content was only 0.92 mol% (benzyl bromination rate: 5.6%), which is not only an extremely low bromination rate, but also contains a large amount of brominated n-hexane. (2) Ionization reaction 50 g of the supernatant of the brominated polymer solution XDP-IV-1 was added to a 250 mL three-neck flask equipped with a magnetic stirrer and placed in a constant-temperature oil bath. 1.9 mL of 4-ethylpyridine (dissolved in 5 mL of carbon tetrachloride) was added to adjust the molar ratio of pyridine to liquid bromine to 1.1:1, and the reaction was carried out at 80 °C for 10 hours under nitrogen protection. After the reaction was completed, the insoluble micelles were separated from the solvent by filtration, washed twice in acetone, and filtered. The solids were then removed and dried under vacuum at 40 °C to a predetermined weight to obtain the isobutylene-based pyridine salt ionic polymer D-IV-1. The content of pyridine salt functional groups was measured by nuclear magnetic hydrogen spectroscopy, and it was found that all benzyl bromide was converted to pyridine salt, the total content of pyridine salt functional groups was 0.9 mol%, the content of side benzylpyridine salt functional groups was 0.9 mol%, and the main chain contained no tertiary carbon pyridine groups. As a result of measurement, analysis and calculation, the isobutylene-based pyridine salt ionic polymer D-IV-1 contains 0.9 mol % of structural units A, 15.6 mol % of structural units B, and 83.5 mol % of structural units C. Test Example IV

[0271] The isobutylene-based pyridine salt polymer prepared in Example IV-1 was blended with PS to produce an antibacterial plastic, and the antibacterial properties of the antibacterial plastic were tested using Escherichia coli as a gram-negative bacterium and Staphylococcus aureus as a gram-positive bacterium. Using a Polylab OS PTW 16 / 40 twin-screw extruder, an isobutylene-based pyridine salt polymer and PS resin were mixed in a mass ratio of 2:8, melt-extruded at 150°C, and granulated to prepare a 20% antibacterial masterbatch. Subsequently, the antibacterial masterbatch and PS resin were mixed in various ratios, melt-extruded in a twin-screw extruder, and granulated to produce antibacterial plastics with mass contents of isobutylene-based pyridine salt polymer of 1 wt%, 3 wt%, 5 wt%, 7 wt%, and 10 wt%, respectively. Each antibacterial plastic pellet was press-molded at 150°C and 20 MPa for 3 minutes, then cold-pressed at 15 MPa for 10 minutes to obtain a 1 mm thick experimental sheet. After leaving it for 24 hours, the sheet was cut into 20 mm x 20 mm test samples. (1) The samples were placed in a 6-well cell culture plate and sterilized by UV irradiation on both sides for 30 minutes. 1 × 10 6 A 30 μL drop of bacterial suspension (CFU / mL) was placed on the sample surface and covered with a sterilized cover glass disc. The suspension was then evenly distributed over the sample surface. The 6-well cell culture plate was placed in a 37°C incubator and incubated at a relative humidity of >90%. After 24 h, 2 mL of saline solution was added to each well of the 6-well culture plate using a pipette gun to wash the sample surface. The plate was then sonicated for 1 min to disperse the bacteria. 100 μL of the washing solution was then drawn up using a pipette gun and serially diluted with saline. The appropriate dilution ratio was selected and spread on a nutrient agar plate. The plate was then incubated in a 37°C incubator for 24 h. The plate with a colony count between 30 and 300 was selected, and the viable bacterial count on the sample surface was calculated, along with the antibacterial rate (R). The results are shown in Table IV-3. R = [(AB) / A] × 100% A is the number of viable bacteria on the surface of a plastic sample to which no antibacterial agent has been added, and B is the number of viable bacteria on the surface of an antibacterial plastic sample. [Table 18] (2) Six antibacterial plastic samples were weighed and placed in Erlenmeyer flasks. In accordance with GB / T16886.12-2005, deionized water was added at a rate of 0.1 g / mL. The samples were then placed in a 37°C water bath shaker and shaken at a speed of 150 r / min. The samples were then immersed for 15 and 30 days before being tested for antibacterial properties. The test methods were the same as above. The results after 15 days of immersion are shown in Table IV-4, and the results after 30 days of immersion are shown in Table IV-5. [Table 19] [Table 20] From the above results, it was found that when the isobutylene-based pyridine salt ionic polymer prepared in Example IV-1 is blended with PS as an antibacterial agent to produce antibacterial plastic, if the amount used is 5 parts or more, a good antibacterial effect is exhibited, with the 24-hour antibacterial rate against gram-negative and gram-positive bacteria reaching 90% or more, and the antibacterial plastic maintains a good antibacterial effect even when immersed in water for 15 to 30 days.

Claims

1. An isobutylene-based cation salt ionic polymer, the polymer comprising structural unit A, structural unit B, and structural unit C; The structural unit A has a structure represented by formula (2) and / or formula (3), and optionally a structure represented by formula (1), the structural unit B has a structure represented by formula (4), and the structural unit C has a structure represented by formula (5). An isobutylene-based cation salt ionic polymer. 【Chemical 1】 (However, R １ is C １ ~C ４ and R ２ is C １ ~C ４ is an alkyl of Q is, 【Chemistry 2】 and Here, R ３ , R ４ , R ５ are each independently C １ ~C ２０ Straight chain alkyl of C １ ~C ２０ or a branched alkyl of C ６ ~C ２０ is an aryl of R ６ , R ７ , R ８ are each independently C １ ~C １０ Straight chain alkyl of C １ ~C １０ Branched alkyl of C ３ ~C １０ cycloalkyl, or C ６ ~C １０ is an aryl of R ９ is hydrogen, C １ ~C ２０ is a linear alkyl of R １０ , R １１ , R １２ are each independently hydrogen, a halogen atom, or C １ ~C １０ Straight chain alkyl of C １ ~C １０ Branched alkyl, hydroxy, nitro, -(CH ２ ) ｎ -NH ２ , cyano, or C ６ ~C １０ and n is an integer from 0 to 5; R １３ , R １４ , R １５ , R １６ , R １７ are each independently hydrogen, a halogen atom, or C １ ~C ２０ Straight chain alkyl of C １ ~C ２０ branched alkyl, nitro, amino, or cyano; X is Cl or Br.

2. R １ is methylene or ethylene, preferably methylene, and R ２ is methyl or ethyl, preferably methyl, and R ３ , R ４ , R ５ are each independently C １ ~C １８ or a straight chain alkyl of C ６ ~C ９ aryl, preferably methyl, C ８ ~C １６ or phenyl, and X is Br; Preferably, R １ is methylene or ethylene, preferably methylene, and R ２ is methyl or ethyl, preferably methyl, and R ６ , R ７ , R ８ are each independently C １ ~C ８ Straight chain alkyl of C ５ ~C ８ Cycloalkyl C ６ ~C ８ aryl, preferably C １ ~C ８ , cyclopentyl, cyclohexyl, or phenyl; X is Br; Preferably, R １ is methylene or ethylene, preferably methylene, and R ２ is methyl or ethyl, preferably methyl, and R ９ is hydrogen, C １ ~C １８ linear alkyl, preferably hydrogen, C １ ~C １６ is a linear alkyl of R １０ , R １１ , R １２ are each independently hydrogen, a halogen atom, or C １ ~C ５ Straight chain alkyl of C １ ~C ５ Branched alkyl, hydroxy, nitro, -(CH ２ ) ｎ -NH ２ , cyano, or C ６ ~C ８ n is an integer of 0 to 3, and preferably each independently represents a hydrogen atom, a halogen atom, or C １ ~C ４ , hydroxy, nitro, cyano, amino, or phenyl, and X is Br; Preferably, R １ is methylene or ethylene, preferably methylene, and R ２ is methyl or ethyl, preferably methyl, and R １３ , R １４ , R １５ , R １６ , R １７ are each independently hydrogen, halogen, or C １ ~C １５ Straight chain alkyl of C １ ~C １５ branched alkyl, nitro, amino, or cyano, preferably hydrogen, halogen, C １ ~C １０ 2. The isobutylene-based cationic salt ionic polymer of claim 1, wherein X is a linear alkyl, amino, or cyano; and X is Br.

3. Based on the total molar amount of the polymer, the content of cationic salt functional groups is 1.5 to 35 mol%, preferably 2.5 to 25 mol%; Preferably, Q is 【Chemistry 3】 when the content of cation salt functional groups is 1.5 to 35 mol%, preferably 2.5 to 25 mol%, based on the total molar amount of the polymer; Preferably, Q is 【Chemistry 4】 the content of cation salt functional groups is 1.5 to 23 mol%, preferably 3 to 18 mol%, based on the total molar amount of the polymer; Preferably, Q is 【Chemistry 5】 the content of cation salt functional groups is 1.5 to 23 mol%, preferably 3 to 18 mol%, based on the total molar amount of the polymer; Preferably, Q is 【Chemistry 6】 3. The isobutylene-based cation salt ionic polymer according to claim 1, wherein the content of cation salt functional groups is 1.5 to 35 mol%, preferably 3 to 25 mol%, based on the total molar amount of the polymer.

4. Based on the total molar amount of the polymer, the content of side chain benzyl cation salt functional groups is 1 to 20 mol%, preferably 1.5 to 15 mol%, and the content of main chain tertiary carbocation salt functional groups is 0.5 to 15 mol%, preferably 1 to 10 mol%; Preferably, Q is 【Chemistry 7】 In this case, the content of side benzyl cation salt functional groups is 1 to 20 mol%, preferably 1.5 to 15 mol%, and the content of main chain tertiary carbocation salt functional groups is 0.5 to 15 mol%, preferably 1 to 10 mol%, based on the total molar amount of the polymer; Preferably, Q is 【Chemistry 8】 where, based on the total molar amount of the polymer, the content of side group benzyl cation salt functional groups is 1 to 15 mol%, preferably 2 to 13 mol%, and the content of main chain tertiary carbocation salt functional groups is 0.5 to 8 mol%, preferably 1 to 5 mol%, based on the total molar amount of the polymer; Preferably, Q is 【Chemistry 9】 In this case, the content of side benzyl cation salt functional groups is 1 to 15 mol%, preferably 2 to 13 mol%, and the content of main chain tertiary carbocation salt functional groups is 0.5 to 8 mol%, preferably 1 to 5 mol%, based on the total molar amount of the polymer; Preferably, Q is 【Chemistry 10】 wherein the content of pendant benzyl cation salt functional groups is 1 to 20 mol%, preferably 2 to 15 mol%, and the content of main chain tertiary carbocation salt functional groups is 0.5 to 15 mol%, preferably 1 to 10 mol%, based on the total molar amount of the polymer.

5. Based on the total molar amount of the polymer, the content of the structural unit A is 1 to 20 mol %, the content of the structural unit B is 0.5 to 10 mol %, and the content of the structural unit C is 75 to 97 mol %; Preferably, the content of the structural unit A is 2 to 15 mol %, the content of the structural unit B is 1 to 5 mol %, and the content of the structural unit C is 80 to 95 mol %, based on the total molar amount of the polymer. The isobutylene-based cation salt ionic polymer according to any one of claims 1 to 4.

6. The thermal decomposition temperature of the isobutylene-based cation salt polymer is 150 to 550°C, preferably 180 to 500°C, Preferably, the isobutylene-based cation salt polymer is an isobutylene-based quaternary ammonium salt polymer, and the thermal decomposition temperature of the isobutylene-based quaternary ammonium salt polymer is 150 to 500°C, preferably 180 to 450°C; Preferably, the isobutylene-based cation salt polymer is an isobutylene-based quaternary phosphonium salt polymer, and the thermal decomposition temperature of the isobutylene-based quaternary phosphonium salt ionic polymer is 150 to 500°C, preferably 200 to 450°C; Preferably, the isobutylene-based cation salt polymer is an isobutylene-based imidazole salt polymer, and the thermal decomposition temperature of the isobutylene-based imidazole salt ionic polymer is 150 to 550°C, preferably 200 to 500°C; Preferably, the isobutylene-based pyridine salt ionic salt is an isobutylene-based pyridine salt ionic salt, and the thermal decomposition temperature of the isobutylene-based pyridine salt ionic polymer is 100 to 500°C, preferably 150 to 450°C. The isobutylene-based cation salt ionic polymer according to any one of claims 1 to 5.

7. The isobutylene-based cation salt ionic polymer has a 5 wt % thermal weight loss temperature of 170° C. or higher, preferably 180° C. or higher; Preferably, the isobutylene-based cation salt polymer is an isobutylene-based quaternary ammonium salt polymer, and the 5 wt % thermal weight loss temperature of the isobutylene-based quaternary ammonium salt ionic polymer is 170°C or higher, preferably 180°C or higher; Preferably, the isobutylene-based cation salt polymer is an isobutylene-based quaternary phosphonium salt ionic polymer, and the 5 wt % thermal weight loss temperature of the isobutylene-based quaternary phosphonium salt ionic polymer is 200°C or higher, preferably 220°C or higher; Preferably, the isobutylene-based cation salt polymer is an isobutylene-based imidazole salt ionic polymer, and the 5 wt % thermal weight loss temperature of the isobutylene-based imidazole salt ionic polymer is 200°C or higher, preferably 220°C or higher; The isobutylene-based cation salt ionic polymer according to any one of claims 1 to 6, wherein the isobutylene-based cation salt polymer is an isobutylene-based pyridine salt ionic polymer, and the 5 wt% thermal weight loss temperature of the isobutylene-based pyridine salt ionic polymer is 180°C or higher, preferably 200°C or higher.

8. 1. A method for preparing an isobutylene-based cationic salt ionic polymer, the method comprising: Step (1) of dissolving a polymer in an organic solvent to obtain a polymer solution, and adding a halogen to the polymer solution to perform a halogenation reaction to obtain a halogenated polymer solution; and (2) adding at least one of a tertiary amine compound, a tertiary phosphine compound, an imidazole compound, and a pyridine compound to the halogenated polymer solution to carry out an ionization reaction, thereby obtaining the isobutylene-based cation salt ionic polymer; the polymer is a random copolymer of isobutylene and alkylstyrene; The method for preparing an isobutylene-based cationic salt ionic polymer, characterized in that the halogenation reaction is carried out under irradiation with visible light, and the visible light mode is pulsed emission.

9. Based on the total molar amount of the polymer, the content of structural units provided by alkylstyrene is 3 to 25 mol%, preferably 5 to 20 mol%, and the content of structural units provided by isobutylene is 75 to 97 mol%, preferably 80 to 95 mol%; Preferably, the polymer has a weight average molecular weight M ｗ is 1 x 10 ４ ~1 x 10 ５ , preferably 2 × 10 ４ ~8 x 10 ４ and the molecular weight distribution coefficient is 2 to 3.5, preferably 2.2 to 3; 9. A preparation method according to claim 8, wherein the content of aluminum ions in the polymer is preferably less than 10 ppm, preferably less than 5 ppm.

10. the wavelength of the visible light is 560 to 630 nm; The preparation method according to claim 8 or 9, wherein the pulse time of the pulsed light emission is preferably 5 to 40 s, more preferably 10 to 30 s.

11. The molar ratio of the polymer to the halogen is 1:0.5-2, preferably 1:0.8-1.5, based on the molar content of the structural units provided by the alkylstyrene; Preferably, the halogen is liquid bromine; Preferably, a halogen solution is obtained by mixing a halogen with an organic solvent, and the halogen solution is added dropwise to the polymer solution to carry out a halogenation reaction; The method according to any one of claims 8 to 10, wherein the dropping speed of the halogen solution is preferably controlled so that the halogenation reaction time is 30 to 180 min.

12. The tertiary amine compound has a structure represented by formula (6): Preferably, the tertiary phosphine compound has a structure represented by formula (7): Preferably, the imidazole compound has a structure represented by formula (8): Preferably, the pyridine compound has a structure represented by formula (9): The preparation method according to any one of claims 8 to 11. 【Chemistry 11】 (However, R ３ , R ４ , R ５ are each independently C １ ~C ２０ Straight chain alkyl of C １ ~C ２０ or a branched alkyl of C ６ ~C ２０ is an aryl of 【Chemistry 12】 (However, R ６ , R ７ , R ８ are each independently C １ ~C １０ Straight chain alkyl of C １ ~C １０ Branched alkyl of C ３ ~C １０ cycloalkyl, or C ６ ~C １０ is an aryl of 【Chemistry 13】 (However, R ９ is hydrogen, C １ ~C ２０ is a linear alkyl group of R １０ , R １１ , R １２ are each independently hydrogen, a halogen atom, or C １ ~C １０ Straight chain alkyl of C １ ~C １０ Branched alkyl, hydroxy, nitro, -(CH ２ ) ｎ -NH ２ , cyano, or C ６ ~C １０ and n is an integer of 0 to 5. 【Chemistry 14】 (However, R １３ , R １４ , R １５ , R １６ , R １７ are each independently hydrogen, a halogen atom, or C １ ~C ２０ Straight chain alkyl of C １ ~C ２０ branched alkyl, nitro, amino, or cyano; Preferably, R ３ , R ４ , R ５ are each independently C １ ~C １８ or a straight chain alkyl of C ６ ~C ９ and more preferably R ３ , R ４ , R ５ are each independently methyl, C ８ ~C １６ or phenyl, and more preferably R ３ , R ４ is methyl, and R ５ is C ８ ~C １６ or phenyl, Preferably, R ６ , R ７ , R ８ are each independently C １ ~C ８ Straight chain alkyl of C ５ ~C ８ Cycloalkyl C ６ ~C ８ aryl, more preferably R ６ , R ７ , R ８ are each independently C １ ~C ８ cyclopentyl, cyclohexyl, or phenyl; Preferably, R ９ is hydrogen, C １ ~C １８ is a linear alkyl group of R １０ , R １１ , R １２ are each independently hydrogen, a halogen atom, or C １ ~C ５ Straight chain alkyl of C １ ~C ５ Branched alkyl, hydroxy, nitro, -(CH ２ ) ｎ -NH ２ , cyano, or C ６ ~C ８ and n is an integer of 0 to 3, more preferably R ９ is hydrogen, C １ ~C １６ is a linear alkyl group of R １０ , R １１ , R １２ are each independently hydrogen, a halogen atom, or C １ ~C ４ straight chain alkyl, hydroxy, nitro, cyano, amino, or phenyl; Preferably, R １３ , R １４ , R １５ , R １６ , R １７ are each independently hydrogen, halogen, or C １ ~C １５ Straight chain alkyl of C １ ~C １５ branched alkyl, nitro, amino, or cyano, and more preferably R １３ , R １４ , R １５ , R １６ , R １７ are each independently hydrogen, halogen, or C １ ~C １０ is a straight chain alkyl, amino, or cyano.

13. The preparation method according to any one of claims 8 to 12, wherein the molar ratio of at least one of the tertiary amine compound, tertiary phosphine compound, imidazole compound, and pyridine compound to the halogen is 0.8 to 1.5:1, preferably 0.9 to 1.2:

1.

14. In step (2), the ionization reaction conditions include: under the protection of a protective gas, a reaction temperature of 20 to 150°C, preferably 40 to 120°C, and a reaction time of 1 to 24 hours, preferably 2 to 20 hours; Preferably, the ionization reaction conditions include: under the protection of a protective gas, a reaction temperature of 20 to 100°C, preferably 40 to 80°C, and a reaction time of 1 to 10 hours, preferably 2 to 8 hours; Preferably, the ionization reaction conditions include: in the presence of a protective gas, a reaction temperature of 60 to 150°C, preferably 80 to 120°C, and a reaction time of 4 to 24 hours, preferably 6 to 20 hours; Preferably, the ionization reaction conditions include: in the presence of a protective gas, a reaction temperature of 60 to 120°C, preferably 70 to 100°C, and a reaction time of 6 to 20 hours, preferably 8 to 16 hours; The preparation method according to any one of claims 8 to 13, wherein the ionization reaction conditions preferably include: in the presence of a protective gas, a reaction temperature of 60 to 150°C, preferably 80 to 120°C, and a reaction time of 4 to 20 hours, preferably 6 to 16 hours.

15. An isobutylene-based cationic salt ionic polymer prepared by the preparation method according to any one of claims 8 to 14, Preferably, the isobutylene-based cation salt ionic polymer is at least one selected from the group consisting of an isobutylene-based quaternary ammonium salt ionic polymer, an isobutylene-based quaternary phosphonium salt ionic polymer, an isobutylene-based imidazole salt ionic polymer, and an isobutylene-based pyridine salt ionic polymer.

16. Use of the isobutylene-based cationic salt ionic polymer according to any one of claims 1 to 7 and 15 as an antibacterial agent.

17. 20. Use of the isobutylene-based cationic salt ionic polymer of any one of claims 1 to 7 and 15 in inhibiting and killing at least one of bacteria, fungi, and viruses.

18. An antibacterial polymeric material, The antibacterial polymer material comprises an isobutylene-based cation salt ionic polymer according to any one of claims 1 to 7 and 15; Preferably, the amount of the isobutyl cation salt ionic polymer used is 1 to 10 parts, preferably 2 to 7 parts, based on 100 parts of the polymer material; Preferably, the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary ammonium salt ionic polymer, and the amount of the isobutylene-based quaternary ammonium salt ionic polymer used is 1 to 10 parts, preferably 5 to 7 parts, per 100 parts of the polymer material; Preferably, the isobutylene-based cation salt ionic polymer is an isobutylene-based quaternary phosphonium salt ionic polymer, and the amount of the isobutylene-based quaternary phosphonium salt ionic polymer used is 1 to 8 parts, preferably 2 to 6 parts, based on 100 parts of the polymer material; Preferably, the isobutylene-based cation salt ionic polymer is an isobutylene-based imidazole salt ionic polymer, and the amount of the isobutylene-based imidazole salt ionic polymer used is 1 to 10 parts, preferably 3 to 7 parts, per 100 parts of the polymer material; Preferably, the isobutylene-based cation salt ionic polymer is an isobutylene-based pyridine salt ionic polymer, and the amount of the isobutylene-based pyridine salt ionic polymer used is 1 to 10 parts, preferably 3 to 7 parts, per 100 parts of the polymer material; Preferably, the antibacterial polymer material is at least one selected from the group consisting of plastic, rubber, fiber, and paint.

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